U.S. patent application number 16/078612 was filed with the patent office on 2019-02-14 for laminate and application for same.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. The applicant listed for this patent is MITSUI CHEMICALS, INC.. Invention is credited to Kotaro ICHINO, Yoshiharu KIKUCHI.
Application Number | 20190047264 16/078612 |
Document ID | / |
Family ID | 59743030 |
Filed Date | 2019-02-14 |
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United States Patent
Application |
20190047264 |
Kind Code |
A1 |
KIKUCHI; Yoshiharu ; et
al. |
February 14, 2019 |
LAMINATE AND APPLICATION FOR SAME
Abstract
The layered product includes at least one type of layer selected
from the layers (1) and (2), and at least one type of layer
selected from the layers (3) and (4), in which at least one layer
of the at least one type of layer selected from the layers (1) and
(2) is directly in contact with or adjacent via an adhesive layer
to at least one layer of the at least one type of layer selected
from the layers (3) and (4): layer (1): a layer prepared using an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer; layer
(2): a layer prepared using an ethylene/carboxylic acid copolymer;
layer (3): a layer prepared using an acrylic-type rubber; and layer
(4): a layer prepared using a halogen-containing polymer.
Inventors: |
KIKUCHI; Yoshiharu;
(Ichihara-shi, Chiba, JP) ; ICHINO; Kotaro;
(Ichihara-shi, Chiba, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MITSUI CHEMICALS, INC. |
Tokyo |
|
JP |
|
|
Assignee: |
MITSUI CHEMICALS, INC.
Tokyo
JP
|
Family ID: |
59743030 |
Appl. No.: |
16/078612 |
Filed: |
March 1, 2017 |
PCT Filed: |
March 1, 2017 |
PCT NO: |
PCT/JP2017/008112 |
371 Date: |
August 21, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 25/042 20130101;
C08K 5/0025 20130101; C08K 3/26 20130101; B32B 2597/00 20130101;
B32B 25/16 20130101; F16L 11/04 20130101; C08F 2800/20 20130101;
B32B 27/32 20130101; C08J 5/12 20130101; F16L 11/125 20130101; C08J
2427/20 20130101; B32B 2250/248 20130101; C08K 3/22 20130101; B32B
27/28 20130101; B32B 27/00 20130101; F02M 35/10157 20130101; F02M
35/10137 20130101; C08K 5/19 20130101; B32B 7/10 20130101; B32B
7/12 20130101; B32B 27/08 20130101; B32B 27/26 20130101; B32B 1/08
20130101; C08J 2323/16 20130101; C08J 2433/06 20130101; F02M
37/0017 20130101; F02M 35/10321 20130101; B32B 2250/02 20130101;
B32B 2264/102 20130101; B32B 25/14 20130101; C08F 210/18 20130101;
B32B 25/08 20130101; C09K 3/1009 20130101; C08K 5/19 20130101; C08L
23/0869 20130101; C08K 3/26 20130101; C08L 23/0869 20130101; C08K
5/19 20130101; C08L 23/16 20130101; C08K 3/26 20130101; C08L 23/16
20130101; C08K 3/22 20130101; C08L 23/16 20130101; C08K 3/22
20130101; C08L 23/0869 20130101; C08K 3/26 20130101; C08L 27/12
20130101; C08K 5/19 20130101; C08L 27/12 20130101 |
International
Class: |
B32B 25/08 20060101
B32B025/08; B32B 7/12 20060101 B32B007/12; B32B 27/32 20060101
B32B027/32; B32B 25/14 20060101 B32B025/14; B32B 27/08 20060101
B32B027/08; C08F 210/18 20060101 C08F210/18; C08J 5/12 20060101
C08J005/12; F16L 11/12 20060101 F16L011/12 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 4, 2016 |
JP |
2016-042340 |
Claims
1. A layered product comprising at least one type of layer selected
from the following layers (1) and (2) and at least one type of
layer selected from the following layers (3) and (4), wherein at
least one layer of the at least one type of layer selected from the
layers (1) and (2) is directly in contact with or adjacent via an
adhesive layer to at least one layer of the at least one type of
layer selected from the layers (3) and (4): layer (1): a layer
prepared using an ethylene/.alpha.-olefin/non-conjugated polyene
copolymer; layer (2): a layer prepared using an ethylene/carboxylic
acid copolymer; layer (3): a layer prepared using an acrylic-type
rubber; and layer (4): a layer prepared using a halogen-containing
polymer.
2. The layered product according to claim 1, wherein the at least
one type of layer selected from the layers (1) and (2) contains 0.2
parts by mass or more of an onium salt with respect to 100 parts by
mass of the copolymer, and further contains 7 parts by mass or more
of an inorganic compound containing oxygen and at least one element
selected from Group 2 elements and Group 13 elements with respect
to 100 parts by mass of the copolymer.
3. The layered product according to claim 1, wherein the at least
one type of layer selected from the layer (1) and the layer (2)
contains from 0.2 parts by mass to 10 parts by mass of an onium
salt with respect to 100 parts by mass of the copolymer, and
further contains from 7 parts by mass to 100 parts by mass of an
inorganic compound containing oxygen and at least one element
selected from Group 2 elements and Group 13 elements with respect
to 100 parts by mass of the copolymer.
4. The layered product according to claim 1, wherein the layer (1)
and the layer (4) are directly in contact with each other.
5. The layered product according to claim 1, wherein the at least
one type of layer selected from the layers (1) and (2) is bonded to
the layer (3) via the adhesive layer.
6. The layered product according to claim 1, wherein the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer satisfies
the following requirements (I) to (III): requirement (I): a molar
ratio of a structural unit derived from ethylene and a structural
unit derived from .alpha.-olefin (ethylene/.alpha.-olefin) is from
40/60 to 99.9/0.1; requirement (II): a structural unit derived from
non-conjugated polyene accounts for 0.07% to 10% by mass with
respect to 100% by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer; and
requirement (III): an intrinsic viscosity [.eta.] measured in
decalin at 135.degree. C. is from 1.0 to 4.0 dl/g.
7. The layered product according to claim 1, wherein the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer has a
structural unit derived from 5-vinyl-2-norbornene (VNB).
8. The layered product according to claim 1, wherein the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer satisfies
the following requirement (IV): requirement (IV): a B value
represented by the following formula (i) is 1.20 or more; B
value=([EX]+2[Y])/[2.times.[E].times.([X]+[Y])] (i) [where [E],
[X], and [Y] represent molar fractions of ethylene, an
.alpha.-olefin, and a non-conjugated polyene, respectively, and
[EX] represents an ethylene-.alpha.-olefin diad chain
fraction].
9. A hose comprising the layered product according to claim 1 as at
least a part thereof.
10. The hose according to claim 9, which is used in any one of
applications for an automobile, a motorbike, industrial machinery,
construction machinery, and agricultural machinery.
11. The hose according to claim 9, which is used for a turbocharger
hose for an automobile.
Description
TECHNICAL FIELD
[0001] The present invention relates to a layered product and a use
thereof.
BACKGROUND ART
[0002] Hoses formed with rubbers for industrial use are required to
have various physical properties such as strength, flexibility,
thermal resistance, bending resistance, and solvent resistance. It
is difficult to satisfy all the required characteristics with one
kind of rubber. For such reason, it is common to use rubbers having
different properties in a stacked manner.
[0003] When different kinds of rubbers are stacked, a polar rubber
may be directly bonded to a different rubber. However, it is common
to bond a non-polar rubber via an adhesive layer.
[0004] Rubber hoses used for an engine of an automobile are
required to have high levels of heat aging resistance, fatigue
resistance, oil resistance, and the like. Therefore, hoses, in
which expensive fluorine and acrylic rubbers are stacked, have been
used. It has been common to bond a fluorine rubber and a non-polar
rubber via an adhesive layer (see, for example, Patent Document 1).
As a method of bonding without an adhesive layer, vulcanization
bonding of a layer comprising a fluorine rubber and a vulcanizing
agent and a layer comprising a non-fluorine rubber and a
vulcanizing agent has been suggested (see, for example, Patent
Document 2).
[0005] In recent years, engines for automobiles are increasingly
downsized and equipped with a turbocharger for improving fuel
efficiency. An engine with a turbocharger is configured so that air
compressed by a compressor wheel is cooled by a charge air cooler
and then sent to the engine, and the compressor wheel is connected
to the charge air cooler by a rubber hose. This turbocharger hose
is required to have high heat aging resistance because air at high
pressure and high temperature (about 180.degree. C.) flows
therethrough. It is also required to have fatigue resistance to
withstand continuous pressure oscillation caused by the passage of
the air. In such an application, a material with high heat aging
resistance such as acrylic rubber and silicone elastomer is
currently adopted.
[0006] Patent Document 3 describes a composition containing an
ethylene/alkyl acrylate copolymer and a cured product of the
composition, which is a product of vulcanizate exhibiting improved
impact fatigue resistance and heat resistance in comparison with
conventional vulcanizates.
[0007] Patent Document 4 proposes a tube-engagement structure
including an innermost rubber layer and an envelope rubber layer,
the innermost layer being made of a fluorocarbon rubber to exhibit
excellent heat resistance and fatigue resistance and protect the
inner layer of tubes from cracking, and the envelope layer being
made of a rubber such as silicone rubber, acrylic rubber, and
ethylene/acrylic-type rubber.
[0008] In addition, it has been usually difficult to bond a
non-polar rubber such as an ethylene/propylene/diene rubber (EPDM)
to a different material. Since EPDM is a non-polar rubber, a method
of stacking layers via an adhesive layer has been common (see for
example, Patent Document 5).
CITATION LIST
Patent Literature
[0009] Patent Literature 1: JP 2005-523181 A
[0010] Patent Literature 2: WO2003/039858 A
[0011] Patent Literature 3: JP 2009-500473 A
[0012] Patent Literature 4: JP 2013-221580 A
[0013] Patent Literature 5: JP 2014-162823 A
SUMMARY OF INVENTION
Technical Problem
[0014] An object of this invention is to provide a layered product
of a non-polar rubber or a rubber having a small polarity which
makes it difficult to bond the rubber with a different material and
a different kind of rubber, which are stacked directly or via an
adhesive layer.
Solution to Problem
[0015] As a result of intensive studies under such circumstances,
the present inventors found the following layered products. This
has led to the completion of this invention.
[0016] In other words, this invention relates to the following [1]
to [11].
[0017] [1] A layered product, which includes at least one type of
layer selected from the following layers (1) and (2) and at least
one type of layer selected from the following layers (3) and
(4),
[0018] wherein at least one layer of the at least one type of layer
selected from the layers (1) and (2) is directly in contact with or
adjacent via an adhesive layer to at least one layer of the at
least one type of layer selected from the layers (3) and (4):
[0019] Layer (1): a layer prepared using an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer
[0020] Layer (2): a layer prepared using an ethylene/carboxylic
acid copolymer
[0021] Layer (3): a layer prepared using an acrylic rubber
[0022] Layer (4): a layer prepared using a halogen-containing
polymer
[0023] [2] The layered product according to [1], wherein the at
least one type of layer selected from the layers (1) and (2)
contains
[0024] 0.2 parts by mass or more of an onium salt with respect to
100 parts by mass of the copolymer, and further contains 7 parts by
mass or more of an inorganic compound containing oxygen and at
least one element selected from Group 2 elements and Group 13
elements with respect to 100 parts by mass of the copolymer.
[0025] [3] The layered product according to [1], wherein the at
least one type of layer selected from the layers (1) and (2)
contains
[0026] from 0.2 parts by mass to 10 parts by mass of an onium salt
with respect to 100 parts by mass of the copolymer, and further
contains from 7 parts by mass to 100 parts by mass of an inorganic
compound containing oxygen and at least one element selected from
Group 2 elements and Group 13 elements with respect to 100 parts by
mass of the copolymer.
[0027] [4] The layered product according to any one of [1] to [3],
wherein the layer (1) and the layer (4) are directly in contact
with each other.
[0028] [5] The layered product according to any one of [1] to [4],
wherein the at least one type of layer selected from the layers (1)
and (2) is bonded to the layer (3) via the adhesive layer.
[0029] [6] The layered product according to any one of [1] to [5],
wherein the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer satisfies the following requirements (I) to (III).
[0030] Requirement (I): a molar ratio of a structural unit derived
from ethylene and a structural unit derived from .alpha.-olefin
(ethylene/.alpha.-olefin) is from 40/60 to 99.9/0.1.
[0031] Requirement (II): a structural unit derived from
non-conjugated polyene accounts for 0.07% to 10% by mass with
respect to 100% by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0032] Requirement (III): an intrinsic viscosity [.eta.] measured
in decalin at 135.degree. C. is from 1.0 to 4.0 dl/g.
[0033] [7] The layered product according to any one of [1] to [6],
wherein the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer has a structural unit derived from 5-vinyl-2-norbornene
(VNB).
[0034] [8] The layered product according to any one of [1] to [7],
wherein the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer satisfies the following requirement (IV).
[0035] Requirement (IV): a B value represented by the following
formula (i) is 1.20 or more.
B value=([EX]+2[Y])/[2.times.[E].times.([X]+[Y])] (i)
[where [E], [X], and [Y] represent molar fractions of ethylene, an
.alpha.-olefin, and a non-conjugated polyene, respectively, and
[EX] represents an ethylene-.alpha.-olefin diad chain fraction]
[0036] [9] A hose comprising the layered product according to any
one of [1] to [8] as at least a part thereof.
[0037] [10] The hose according to [9], which is used in any one of
applications for an automobile, a motorbike, industrial machinery,
construction machinery, and agricultural machinery.
[0038] [11] The hose according to [9], which is used for a
turbocharger hose for an automobile.
Advantageous Effects of Invention
[0039] According to this invention, it is possible to provide a
layered product of a non-polar rubber or a rubber having a small
polarity which makes it difficult to bond the rubber with a
different material and a different kind of rubber, which are
stacked directly or via an adhesive layer.
DESCRIPTION OF EMBODIMENTS
[0040] Hereinafter, this invention will be described in detail.
[Layered Product]
[0041] The layered product of this invention is a layered product,
which includes at least one type of layer selected from the
following layers (1) and (2), and further includes at least one
type of layer selected from the following layers (3) and (4),
wherein at least one layer of the at least one type of layer
selected from the layers (1) and (2) is directly in contact with or
adjacent via an adhesive layer to at least one layer of the at
least one type of layer selected from the layers (3) and (4).
[0042] Layer (1): a layer prepared using an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer
[0043] Layer (2): a layer prepared using an ethylene/carboxylic
acid copolymer
[0044] Layer (3): a layer prepared using an acrylic rubber
[0045] Layer (4): a layer prepared using a halogen-containing
polymer
[0046] Hereinafter, the layered product of this invention will be
described in detail after describing each of polymers used for
preparing the layers (1) to (4).
[0047] (Ethylene/.alpha.-Olefin/Non-Conjugated Polyene
Copolymer)
[0048] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
has structural units derived from ethylene, an .alpha.-olefin, and
a non-conjugated polyene.
[0049] As an .alpha.-olefin, .alpha.-olefin having 3 to 20 carbon
atoms is preferable. Examples of an .alpha.-olefin include, for
example, propylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, and 1-eicosene. Among them,
.alpha.-olefins having 3 to 8 carbon atoms are preferable, such as
propylene, 1-butene, 1-hexene, and 1-octene, and in particular,
propylene is preferable. Such .alpha.-olefins are preferable
because they are relatively inexpensive in raw material cost, and
provide not only an ethylene/.alpha.-olefin/non-conjugated polyene
copolymer excellent in mechanical properties but also a layered
product exhibiting rubber elasticity. These .alpha.-olefins may be
used singly or in combination of the two or more kinds.
[0050] In other words, the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer contains a structural unit derived from at least
one kind of .alpha.-olefin, and may contain a structural unit
derived from two or more kinds of .alpha.-olefins.
[0051] Examples of a non-conjugated polyene include
5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene,
dicyclopentadiene, 5-ethylidene-2-norbornene (ENB),
5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene,
5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene,
5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene,
5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene,
5-(2,3-dimethyl-3-butenyl)-2-norbornene,
5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene,
5-(3-methyl-5-hexenyl)-2-norbornene,
5-(3,4-dimethyl-4-pentenyl)-2-norbornene,
5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene,
5-(2-methyl-6-heptenyl)-2-norbornene,
5-(1,2-dimethyl-5-hexenyl)-2-norbornene,
5-(5-ethyl-5-hexenyl)-2-norbornene,
5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene.
[0052] The non-conjugated polyenes may be used singly or in
combination of the two or more kinds.
[0053] In other words, the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer contains a structural unit derived from at least
one kind of non-conjugated polyene, and may contain a structural
unit derived from two or more kinds of non-conjugated polyenes.
[0054] A non-conjugated polyene is preferably VNB from the
viewpoint that it is easily available and excellent in crosslinking
reactivity with organic peroxide during its crosslinking reaction
after polymerization, enabling a layered product to have excellent
thermal resistance and fatigue resistance. In other words, it is
preferable for the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer to have a VNB-derived structural unit. A VNB-derived
structural unit in the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer accounts for preferably from 0.07% to 10% by
mass, more preferably from 0.1% to 8.0% by mass, and most
preferably from 0.5% to 5.0% by mass with respect to 100% by mass
of the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer.
[0055] In addition, a non-conjugated polyene is preferably ENB from
the viewpoint that it is easily available and excellent in
crosslinking reactivity with sulfur or a vulcanization enhancer
during its crosslinking reaction after polymerization, facilitating
control of the crosslinking rate and achievement of favorable
mechanical physical properties. In other words, it is preferable
for the ethylene/.alpha.-olefin/non-conjugated polyene copolymer to
have an ENB-derived structural unit.
[0056] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
satisfies preferably at least one of the following requirements (I)
to (III), more preferably two of the following requirements (I) to
(III), and particularly preferably the requirements (I) to
(III).
[0057] Requirement (I): a molar ratio of a structural unit derived
from ethylene and a structural unit derived from an .alpha.-olefin
(ethylene/.alpha.-olefin) is from 40/60 to 99.9/0.1.
[0058] Requirement (II): a structural unit derived from a
non-conjugated polyene accounts for 0.07% to 10% by mass with
respect to 100% by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0059] Requirement (III): an intrinsic viscosity [.eta.] measured
in decalin at 135.degree. C. is from 1.0 to 4.0 dl/g.
[0060] (Requirement (I))
[0061] Requirement (I) is to specify that a molar ratio of a
structural unit derived from ethylene and a structural unit derived
from an .alpha.-olefin (ethylene/.alpha.-olefin) is from 40/60 to
99.9/0.1.
[0062] The molar ratio of a structural unit derived from ethylene
and a structural unit derived from an .alpha.-olefin
(ethylene/.alpha.-olefin) is preferably from 55/45 to 85/15 and
more preferably from 55/45 to 78/22.
[0063] When the ethylene/.alpha.-olefin ratio falls within the
above range, a layer comprising a crosslinked article which is
obtained by crosslinking an ethylene/.alpha.-olefin/non-conjugated
polyene copolymer not only exhibits excellent rubber elasticity,
but also is excellent in mechanical strength and flexibility. In
addition, the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer not only exhibits excellent rubber elasticity, but also
is excellent in mechanical strength and flexibility within the
above range, which is preferable.
[0064] The molar ratio of a structural unit derived from ethylene
and a structural unit derived from an .alpha.-olefin in the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer can be
determined by using .sup.13C-NMR.
[0065] (Requirement (II))
[0066] Requirement (II) is to specify that a structural unit
derived from a non-conjugated polyene accounts for 0.07% to 10% by
mass with respect to 100% by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0067] The amount of a structural unit derived from a
non-conjugated polyene accounts for preferably from 0.1% to 8.0% by
mass and particularly preferably from 0.5% to 5.0% by mass. The
ethylene/.alpha.-olefin/non-conjugated polyene copolymer having a
structural unit derived from a non-conjugated polyene within the
above range is preferable because it has sufficient hardness and
excellent mechanical strength, and such
ethylene/.alpha.-olefin/non-conjugated polyene copolymer is also
preferable because it enables obtaining a crosslinked article
having a large crosslinking density such that hardness of a layer
comprising the crosslinked article can be improved.
[0068] The amount of a structural unit derived from a
non-conjugated polyene can be determined by using .sup.13C-NMR.
[0069] (Requirement (III))
[0070] Requirement (III) is to specify that an intrinsic viscosity
[.eta.] of the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer measured in decalin at 135.degree. C. is from 1.0 to 4.0
dl/g.
[0071] The intrinsic viscosity [.eta.] is more preferably from 1.5
to 4.0 dl/g. When the intrinsic viscosity is within the above
range, a favorable balance between physical properties and
processability is achieved, which is preferable.
[0072] Intrinsic viscosity can be measured by the method described
in the Examples.
[0073] In addition, the ethylene/.alpha.-olefin/non-conjugated
polyene preferably satisfies the following requirement (IV).
[0074] (Requirement (IV))
[0075] Requirement (IV) is to specify that a B value expressed by
the following formula (i) for the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer is 1.20 or
more.
B value=([EX]+2[Y])/[2.times.[E].times.([X]+[Y])] (i)
[where [E], [X], and [Y] represent molar fractions of ethylene, an
.alpha.-olefin, and a non-conjugated polyene, respectively, and
[EX] represents an ethylene-.alpha.-olefin diad chain fraction]
[0076] The B value is more preferably from 1.20 to 1.40 and
particularly preferably from 1.20 to 1.25.
[0077] When the B value is within the above range, the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer has a low
compression permanent set at low temperature, and thus, an
excellent balance between rubber elasticity at low temperature and
tensile strength at ordinary temperature is achieved, which is
preferable.
[0078] In a case in which the B value of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer is 1.20 or
more, and the non-conjugated polyene is VNB, the layered product of
this invention tends to have particularly excellent fatigue
resistance, which is preferable.
[0079] Note that the B value is an index showing random nature of
copolymerized monomer sequence distribution in the copolymer, and
[E], [X], [Y], and [EX] in the above formula (i) can be obtained by
.sup.13C-NMR spectral measurement based on the report of J. C.
Randall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules,
10, 773 (1977)], et al.
[0080] The amount of an .alpha.-olefin (content of a structural
unit derived from an .alpha.-olefin) and the amount of a
non-conjugated polyene (content of a structural unit derived from a
non-conjugated polyene) in the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer can be
determined by using .sup.13C-NMR.
[0081] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
has a structural unit derived from ethylene, a structural unit
derived from an .alpha.-olefin, and a structural unit derived from
a non-conjugated polyene as described above. However, it may have a
structural unit derived from a different monomer (a monomer other
than ethylene, an .alpha.-olefin, and a non-conjugated polyene)
within a range unharmful to the effects of this invention. A
structural unit derived from a different monomer accounts for
preferably 30% by mass or less, more preferably 25% by mass or
less, and particularly preferably 20% by mass or less of 100% by
mass with respect to the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer. Examples of such different monomer include
styrene and acetic acid vinyl.
[0082] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
also has a weight-average molecular weight (Mw) within a range
preferably from 10,000 to 600,000, more preferably from 30,000 to
500,000, and still more preferably from 50,000 to 400,000. The
molecular weight distribution (Mw/Mn) of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer is
preferably from 1.8 to 30, more preferably from 1.8 to 25.0, still
more preferably from 2.0 to 20.0. Mw and Mw/Mn can be obtained as a
numerical value in terms of polystyrene measured by using gel
permeation chromatography (GPC).
[0083] For example, in an application of the layered product of
this invention for a heat-resistant hose, such as a turbocharger
hose for an automobile, an ethylene/.alpha.-olefin/non-conjugated
polyene copolymer having a relatively high molecular weight can be
suitably used, and specifically, an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer having a
weight-average molecular weight (Mw) of 100,000 to 600,000 can be
suitably used.
<Method for Producing Ethylene/.alpha.-Olefin/Non-Conjugated
Polyene Copolymer>
[0084] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
is a copolymer obtained by copolymerizing monomers consisting of
ethylene, an .alpha.-olefin, and a non-conjugated polyene.
[0085] Although the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer of this invention may be prepared by any production
method, it is preferably a copolymer obtained by copolymerizing
monomers in the presence of a metallocene compound, more preferably
a copolymer obtained by copolymerizing monomers in the presence of
a catalyst system containing a metallocene compound.
[0086] (Metallocene Compound)
[0087] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
is desirably a copolymer obtained by copolymerizing monomers in the
presence of at least one kind of metallocene compound selected from
compounds represented by the following general formula [A1]. The
copolymerization of monomers carried out by using a catalyst system
containing such a metallocene compound yields a copolymer
containing suppressed long-chain branching, facilitating preparing
the ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
##STR00001##
[0088] In the above formula [A1], R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.8, R.sup.9, and R.sup.12 are each
independently a hydrogen atom, a hydrocarbon group, a
silicon-containing group, or a heteroatom-containing group other
than any silicon-containing group, and among R.sup.1 to R.sup.4,
adjacent two groups may together form a ring.
[0089] The hydrocarbon group is preferably a hydrocarbon group
having 1 to 20 carbon atoms, and specific examples thereof include
an alkyl group having 1 to 20 carbon atoms, an arylalkyl group
having 7 to 20 carbon atoms, an aryl group or substituted aryl
group having 6 to 20 carbon atoms, and the like. For example, they
include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl,
iso-butyl, sec-butyl, t-butyl, amyl, n-pentyl, neopentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decanyl, 3-methylpentyl,
1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propyl butyl,
1,1-propyl butyl, 1,1-dimethyl-2-methyl propyl,
1-methyl-1-isopropyl-2-methyl propyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, norbornyl, adamantyl, phenyl, o-tolyl,
m-tolyl, p-tolyl, xylyl, isopropylphenyl, t-butylphenyl, naphthyl,
biphenyl, terphenyl, phenanthryl, anthracenyl, benzyl, and cumyl
groups.
[0090] The above hydrocarbon group may have a hydrogen atom
substituted by a halogen atom, and examples thereof include
trifluoromethyl, trifluoromethylphenyl, pentafluorophenyl, and
chlorophenyl groups.
[0091] Examples of the silicon-containing group include silyl,
siloxy, hydrocarbon-substituted silyl, and hydrocarbon-substituted
siloxy groups. For example, they include methylsilyl,
dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl,
triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
dimethylphenylsilyl, dimethyl-t-butylsilyl,
dimethyl(pentafluorophenyl)silyl groups, and the like.
[0092] Examples of heteroatom-containing groups other than
silicon-containing groups include: oxygen-containing groups such as
methoxy, ethoxy, and phenoxy groups; nitrogen-containing groups
such as nitro, cyano, N-methylamino, N,N-dimethylamino, and
N-phenyl amino groups; boron-containing groups such as boranetriyl
and diboranyl groups; and sulfur-containing groups such as sulfonyl
and sulphenyl groups.
[0093] R.sup.6 and R.sup.11 are the same atom or the same group
selected from a hydrogen atom, a hydrocarbon group, a
silicon-containing group, and a heteroatom-containing group other
than any silicon-containing group, R.sup.7 and R.sup.10 are the
same atom or the same group selected from a hydrogen atom, a
hydrocarbon group, a silicon-containing group, and a
heteroatom-containing group other than any silicon-containing
group, R.sup.6 and R.sup.7 may together form a ring, and R.sup.10
and R.sup.11 may together form a ring. However, all of R.sup.6,
R.sup.7, R.sup.10, and R.sup.11 are not a hydrogen atom
simultaneously.
[0094] R.sup.13 and R.sup.14 each independently represent an aryl
group.
[0095] M.sup.1 represents a zirconium atom.
[0096] Y.sup.1 represents a carbon atom or a silicon atom.
[0097] Q represents a halogen atom, a hydrocarbon group, a
halogenated hydrocarbon group, a neutral conjugated or
non-conjugated diene having 4 to 20 carbon atoms, and a neutral
ligand coordinatable by an anionic ligand or a lone pair, and j
represents an integer from 1 to 4, and when j is an integer of two
or more a plurality of Qs may be the same or different from each
other.
[0098] Examples of the halogen atom include a fluorine atom, a
chlorine atom, a bromine atom, and an iodine atom, and the chlorine
atom is preferable.
[0099] The hydrocarbon groups are preferably those having 1 to 10
carbon atoms, and specific examples thereof include methyl, ethyl,
n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl,
2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl,
1,1,2,2-tetramethylpropyl, sec-butyl, t-butyl, 1,1-dimethylbutyl,
1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl,
1-methyl-1-cyclohexyl, benzyl groups, and the like, and methyl,
ethyl, and benzyl groups are preferable.
[0100] Halogenated hydrocarbon groups are preferably halogenated
hydrocarbon groups having 1 to 10 carbon atoms. Specific examples
thereof include trifluoromethyl, trifluoromethylphenyl,
pentafluorophenyl, and chlorophenyl groups.
[0101] The neutral conjugated or non-conjugated diene having 4 to
20 carbon atoms is preferably a neutral conjugated or
non-conjugated diene having 4 to 10 carbon atoms. Specific examples
of the neutral conjugated or non-conjugated diene include s-cis- or
s-trans-.eta.4-1,3-butadiene, s-cis- or
s-trans-.eta.4-1,4-diphenyl-1,3-butadiene, s-cis- or
s-trans-.eta.4-3-methyl-1,3-pentadiene, s-cis- or
s-trans-.eta.4-1,4-dibenzyl-1,3-butadiene, s-cis- or
s-trans-.eta.4-2,4-hexadiene, s-cis- or
s-trans-.eta.4-1,3-pentadiene, s-cis- or
s-trans-.eta.4-1,4-ditoryl-1,3-butadiene, s-cis- or
s-trans-.eta.4-1,4-bis(trimethylsilyl)-1,3-butadiene, and the
like.
[0102] Specific examples of the anionic ligand include alkoxy
groups, such as methoxy, t-butoxy, and phenoxygroups, carboxylate
groups, such as acetate and benzoate groups, and sulfonate groups,
such as mesylate and tosylate groups, and the like.
[0103] Specific examples of the neutral ligand coordinatable by a
lone pair include organic phosphorus compounds, such as
trimethylphosphine, triethylphosphine, triphenylphosphine, and
diphenylmethylphosphine, or ethers, such as tetrahydrofuran,
diethylether, dioxane, and 1,2-dimethoxyethane.
[0104] Examples of the cyclopentadienyl group having substituents
from R.sup.1 to R.sup.4 in the formula [A1] include, but are not
limited to, non-substituted cyclopentadienyl groups having
substituents from R.sup.1 to R.sup.4 which are a hydrogen atom,
cyclopentadienyl groups monosubstituted at position 3, such as
3-t-butylcyclopentadienyl, 3-methylcyclopentadienyl,
3-trimethylsilylcyclopentadienyl, 3-phenylcyclopentadienyl,
3-adamantylcyclopentadienyl, 3-amylcyclopentadienyl, and
3-cyclohexylcyclopentadienyl groups, and cyclopentadienyl groups
disubstituted at positions 3 and 5, such as
3-t-butyl-5-methylcyclopentadienyl,
3-t-butyl-5-ethylcyclopentadienyl,
3-phenyl-5-methylcyclopentadienyl, 3,5-di-t-butylcyclopentadienyl,
3,5-dimethylcyclopentadienyl, 3-phenyl-5-methylcyclopentadienyl,
and 3-trimethylsilyl-5-methylcyclopentadienyl groups. The
non-substituted cyclopentadienyl groups (R.sup.1 to R.sup.4 are a
hydrogen atom) are preferable from the view point of easiness to
synthesize metallocene compounds, and their production cost and
copolymerization ability for non-conjugated polyenes.
[0105] Examples of a fluorenyl group having the substituents from
R.sup.5 to R.sup.12 in the formula [A1] include, but are not
limited to, fluorenyl groups monosubstituted at position 2, such as
2-methylfluorenyl, 2-t-butylfluorenyl, and 2-phenylfluorenyl
groups, fluorenyl groups monosubstituted at position 4, such as
4-methylfluorenyl, 4-t-butylfluorenyl, and 4-phenylfluorenyl
groups, and fluorenyl groups disubstituted at positions 2 and 7 or
3 and 6, such as 2,7-di-t-butylfluorenyl, and
3,6-di-t-butylfluorenyl groups, fluorenyl groups tetrasubstituted
at positions 2, 3, 6, and 7, such as
2,7-dimethyl-3,6-di-t-butylfluorenyl, and
2,7-diphenyl-3,6-di-t-butylfluorenyl groups, and fluorenyl groups
tetrasubstituted at positions 2, 3, 6, and 7 in which R.sup.6
together with R.sup.7 and R.sup.10 together with R.sup.11 each form
a ring, as represented by the formulae [V-I] and [V-II].
##STR00002##
[0106] In the formulae [V-I] and [V-II], R.sup.5, R.sup.8, R.sup.9,
and R.sup.12 are the same as the definitions in the formula
[A1],
[0107] R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f,
R.sup.g, and R.sup.h are each independently a hydrogen atom or an
alkyl group having 1 to 5 carbon atoms, and each may bond to an
adjacent substituent to form together a ring. The alkyl groups are
specifically exemplified by methyl, ethyl, n-propyl, isopropyl,
n-butyl, t-butyl, amyl, and n-pentyl groups. In the formula [V-I],
R.sup.x and R.sup.y are each independently a hydrocarbon group
having 1 to 3 carbon atoms which may have an unsaturated bond,
R.sup.x may form a double-bond together with a carbon atom to which
R.sup.a or R.sup.c bonds, R.sup.y may form a double-bond together
with a carbon atom to which R.sup.e or R.sup.g bonds, and R.sup.x
and R.sup.y are both preferably a saturated or unsaturated
hydrocarbon group having one or two carbon atoms.
[0108] Specific examples of the compounds represented by the
formula [V-I] or [V-II] include octamethyloctahydrodibenzofluorenyl
group represented by the formula [V-III],
tetramethyldodecahydrodibenzofluorenyl group represented by the
formula [V-IV], octamethyltetrahydrodicyclopentafluorenyl group
represented by the formula [V-V],
hexamethyldihydrodicyclopentafluorenyl group represented by the
formula [V-VI], and b, h-dibenzofluorenyl group represented by the
formula [V-VII].
##STR00003##
[0109] A metallocene compound containing any of these fluorenyl
groups and represented by the general formula [A1] is excellent in
copolymerization ability for non-conjugated polyene, and when
Y.sup.1 is a silicon atom, transition metal compounds are
particularly excellent which have any of a fluorenyl group
disubstituted at positions 2 and 7, a fluorenyl group disubstituted
at positions 3 and 6, a fluorenyl group tetrasubstituted at
positions 2, 3, 6, and 7, and a fluorenyl group tetrasubstituted at
positions 2, 3, 6, and 7 represented by the above general formula
[V-I]. When Y is a carbon atom, metallocene compounds are
particularly excellent which have any of a non-substituted
fluorenyl group in which R.sup.5 to R.sup.12 are a hydrogen atom, a
fluorenyl group disubstituted at positions 3 and 6, a fluorenyl
group tetrasubstituted at positions 2, 3, 6, and 7, and a fluorenyl
group tetrasubstituted at position 2, 3, 6, and 7 represented by
the above general formula [V-I].
[0110] In this invention, in a metallocene compound represented by
the general formula [A1], when Y.sup.1 is a silicon atom, with all
substituents from R.sup.5 to R.sup.12 being a hydrogen atom,
R.sup.13 and R.sup.14 are preferably selected from groups other
than methyl, butyl, phenyl, silicon-substituted phenyl, cyclohexyl,
and benzyl groups;
[0111] when Y.sup.1 is a silicon atom, with both R.sup.6 and
R.sup.11 being t-butyl group, and R.sup.5, R.sup.7, R.sup.8,
R.sup.9, R.sup.10, and R.sup.12 not being t-butyl group, R.sup.13
and R.sup.14 are preferably selected from groups other than benzyl
group, and silicon-substituted phenyl group;
[0112] when Y.sup.1 is a carbon atom, with all substituents from
R.sup.5 to R.sup.12 being a hydrogen atom, R.sup.13 and R.sup.14
are preferably selected from groups other than methyl, isopropyl,
t-butyl, isobutyl, phenyl, p-t-butylphenyl, p-n-butylphenyl,
silicon-substituted phenyl, 4-biphenyl, p-tolyl, naphthyl, benzyl,
cyclopentyl, cyclohexyl, and xylyl groups;
[0113] when Y.sup.1 is a carbon atom, with R.sup.6 and R.sup.11
being the same group selected from t-butyl, methyl, and phenyl
groups, and being a different group or atom from R.sup.5, R.sup.7,
R.sup.8, R.sup.9, R.sup.10, and R.sup.12, R.sup.13 and R.sup.14 are
preferably selected from groups other than methyl, phenyl,
p-t-butylphenyl, p-n-butylphenyl, silicon-substituted phenyl, and
benzyl groups;
[0114] when Y.sup.1 is a carbon atom, with R.sup.6 being
dimethylamino, methoxy, or methyl group, and R.sup.5, R.sup.7,
R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 being a
different group or atom from R.sup.6, R.sup.13 and R.sup.14 are
preferably selected from groups other than methyl and phenyl
groups; and
[0115] when Y.sup.1 is a carbon atom, with sites constituted by a
fluorenyl group and substituents from R.sup.5 to R.sup.12 being
b,h-dibenzofluorenyl or a,i-dibenzofluorenyl groups, R.sup.13 and
R.sup.14 are preferably selected from groups other than methyl and
phenyl groups.
[0116] Although specific examples of the metallocene compound
represented by the formula [A1] in this invention will be described
below, the scope of the invention is not particularly limited
thereby.
[0117] Specific examples of the metallocene compound represented by
the formula [A1] in the invention include,
[0118] when Y is a silicon atom, [0119]
diphenylsilylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0120]
diphenylsilylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0121]
diphenylsilylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0122]
diphenylsilylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butyl
fluorenyl)zirconium dichloride, [0123]
diphenylsilylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0124]
diphenylsilylene(cyclopentadienyl)
(tetramethyldodecahydrobenzofluorenyl)zirconium dichloride, [0125]
diphenylsilylene(cyclopentadienyl) (octamethyltetrahydro
dicyclopentafluorenyl)zirconium dichloride, [0126]
diphenylsilylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0127] diphenylsilylene(cyclopentadienyl) (b,h-dibenzofluorenyl)
zirconium dichloride
[0128] di(p-tolyl)silylene(cyclopentadienyl) (fluorenyl)zirconium
dichloride, [0129] di(p-tolyl)silylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0130]
di(p-tolyl)silylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0131]
di(p-tolyl)silylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0132]
di(p-tolyl)silylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0133]
di(p-tolyl)silylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0134]
di(p-tolyl)silylene(cyclopentadienyl)
(tetramethyldodecahydrobenzofluorenyl)zirconium dichloride, [0135]
di(p-tolyl)silylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0136] di(p-tolyl)silylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0137] di(p-tolyl)silylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0138]
di(m-tolyl)silylene(cyclopentadienyl) (fluorenyl)zirconium
dichloride, [0139] di(m-tolyl)silylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0140]
di(m-tolyl)silylene(cyclopentadienyl) (3,6-di-t-butyl
fluorenyl)zirconium dichloride, [0141]
di(m-tolyl)silylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0142]
di(m-tolyl)silylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0143]
di(m-tolyl)silylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0144]
di(m-tolyl)silylene(cyclopentadienyl)
(tetramethyldodecahydrobenzofluorenyl)zirconium dichloride, [0145]
di(m-tolyl)silylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0146] di(m-tolyl)silylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0147] di(m-tolyl)silylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, and the like.
[0148] When Y is a carbon atom, they include [0149]
diphenylmethylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0150]
diphenylmethylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0151]
diphenylmethylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0152]
diphenylmethylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0153]
diphenylmethylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0154] diphenylmethylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0155] diphenylmethylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0156] diphenylmethylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0157]
di(p-tolyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0158]
di(p-tolyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0159]
di(p-tolyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0160]
di(p-tolyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0161]
di(p-tolyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0162]
di(p-tolyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0163] di(p-tolyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0164] di(p-tolyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0165] di(p-tolyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0166]
di(m-tolyl)methylene(cyclopentadienyl) (fluorenyl)zirconium
dichloride, [0167] di(m-tolyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0168]
di(m-tolyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0169]
di(m-tolyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0170]
di(m-tolyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0171]
di(m-tolyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0172]
di(m-tolyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrobenzofluorenyl)zirconium dichloride, [0173]
di(m-tolyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0174] di(m-tolyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0175] di(m-tolyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0176]
di(p-t-butylphenyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0177]
di(p-t-butylphenyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0178]
di(p-t-butylphenyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0179]
di(p-t-butylphenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0180]
di(p-t-butylphenyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0181] di(p-t-butylphenyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0182] di(p-t-butylphenyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0183] di(p-t-butylphenyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0184]
di(4-biphenyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0185]
di(4-biphenyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0186]
di(4-biphenyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0187]
di(4-biphenyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0188]
di(4-biphenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0189]
di(4-biphenyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0190] di(4-biphenyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0191] di(4-biphenyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0192] di(4-biphenyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0193]
di(p-chlorophenyl)methylene(cyclopentadienyl) (fluorenyl) zirconium
dichloride, [0194] di(p-chlorophenyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0195]
di(p-chlorophenyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0196]
di(p-chlorophenyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0197]
di(p-chlorophenyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0198]
di(p-chlorophenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0199]
di(p-chlorophenyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0200] di(p-chlorophenyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0201] di(p-chlorophenyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0202] di(p-chlorophenyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0203]
di(m-chlorophenyl)methylene(cyclopentadienyl) (fluorenyl) zirconium
dichloride, [0204] di(m-chlorophenyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0205]
di(m-chlorophenyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0206]
di(m-chlorophenyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0207]
di(m-chlorophenyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0208]
di(m-chlorophenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0209]
di(m-chlorophenyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0210] di(m-chlorophenyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0211] di(m-chlorophenyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0212] di(m-chlorophenyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0213]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(fluorenyl)zirconium dichloride, [0214]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0215]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0216]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0217]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0218]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0219]
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0220] di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0221] di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0222] di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, [0223]
di(2-naphthyl)methylene(cyclopentadienyl)
(2,7-di-t-butylfluorenyl)zirconium dichloride, [0224]
di(2-naphthyl)methylene(cyclopentadienyl)
(3,6-di-t-butylfluorenyl)zirconium dichloride, [0225]
di(2-naphthyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0226]
di(2-naphthyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, [0227]
di(2-naphthyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, [0228]
di(2-naphthyl)methylene(cyclopentadienyl)
(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride,
[0229] di(2-naphthyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
[0230] di(2-naphthyl)methylene(cyclopentadienyl)
(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride,
[0231] di(2-naphthyl)methylene(cyclopentadienyl)
(b,h-dibenzofluorenyl)zirconium dichloride, and the like.
[0232] The following exemplary structural formulae of these
metallocene compounds depict di(p-tolyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (in the
following formula (A1-1)) and
di(p-chlorophenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (in the
following formula (A1-2)).
##STR00004##
[0233] The above compounds may be used singly or in combination of
the two or more kinds.
[0234] The metallocene compound represented by the formula [A1]
which can be suitably used for preparing the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer of the
invention can be produced by any method without any special
limitation. Specifically, it can be produced, for example, in
accordance with methods described in J. Organomet. Chem., 63,
509(1996), and WO 2005/100410, WO 2006/123759, WO 01/27124, JP
2004-168744 A, JP 2004-175759 A, and JP 2000-212194 A, which are
documents according to the applications by the present
applicants.
[0235] (Catalyst Containing Metallocene Compound)
[0236] Examples of polymerization catalysts which can be suitably
used for producing the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer of this invention include catalysts which contain
the metallocene compound represented by the aforementioned formula
[A1] and are capable of copolymerizing monomers.
[0237] Preferably, they include catalysts consisting of:
[0238] (a) a metallocene compound represented by the aforementioned
formula [A1];
[0239] (b) at least one compound selected from (b-1) an
organometallic compound, (b-2) an organoaluminum oxycompound, and
(b-3) a compound reacting with the metallocene compound (a) to form
an ion pair; and as necessary,
[0240] (c) a particulate carrier.
[0241] Each of the components will be specifically explained
below.
[0242] ((b-1) Organometallic Compound)
[0243] The organometallic compound (b-1) to be used in this
invention is an organometallic compound of Groups 1, 2 and 12, 13
specifically represented by the following general formulae from
[VII] to [IX].
[0244] (b-1a) Organoaluminum Compound Represented by a General
Formula of R.sup.a.sub.mAl(OR.sup.b).sub.nH.sub.pX.sub.q [VII]
[0245] (In the formula [VII], R.sup.a and R.sup.b may be the same
or different from each other, and represent a hydrocarbon group
having 1 to 15 carbon atoms, and preferably 1 to 4 carbon atoms, X
represents a halogen atom, m is a number of 0<m.ltoreq.3, n is a
number of 0.ltoreq.n<3, p is a number of 0.ltoreq.p<3, q is a
number of 0.ltoreq.q<3, and m+n+p+q=3.)
[0246] Such compounds can be exemplified by trialkylaluminums, such
as trimethylaluminum, triethylaluminum, triisobutylaluminum, and
tri-n-octylaluminum, tricycloalkylaluminums, isobutylaluminum
dichloride, diethylaluminum chloride, ethylaluminum dichloride,
ethylaluminum sesquichloride, methylaluminum dichloride,
dimethylaluminum chloride, and diisobutylaluminum hydride.
[0247] (b-1b) Complex Alkylated Product of Group 1 Metal and
Aluminum, Represented by a General Formula of
M.sup.2AlR.sup.a.sub.4 [VIII]
[0248] (In the formula [VIII], M.sup.2 represents Li, Na, or K,
R.sup.a is a hydrocarbon group having 1 to 15 carbon atoms, and
preferably 1 to 4 carbon atoms.)
[0249] Such compounds can be exemplified by
LiAl(C.sub.2H.sub.5).sub.4, LiAl(C.sub.7H.sub.15).sub.4, and the
like.
[0250] (b-1c) Dialkyl Compound Having Group 2 or 12 Metal,
Represented by a General Formula of R.sup.aR.sup.bM.sup.3 [IX]
[0251] (In the formula [IX], Ra and Rb may be the same or different
from each other, and represent a hydrocarbon group having 1 to 15
carbon atoms, and preferably 1 to 4 carbon atoms, and M.sup.3 is
Mg, Zn, or Cd.)
[0252] Among the above organometallic compounds (b-1),
organoaluminum compounds, such as triethylaluminum,
triisobutylaluminum, and tri-n-octylaluminum are preferable. Such
organometallic compounds (b-1) can be used singly or in combination
with the two or more kinds.
[0253] ((b-2) Organoaluminum Oxy-Compound)
[0254] Organoaluminum oxycompounds (b-2) to be used in the
invention may be conventionally well-known aluminoxanes, or
organoaluminum oxycompounds insoluble into benzene as described in
JP H2-78687 A.
[0255] Conventionally known aluminoxanes can be produced, for
example, by the following methods, and usually obtained as a
solution with a hydrocarbon solvent.
[0256] (1) A method in which an organoaluminum compound such as a
trialkylaluminum is added to a hydrocarbon solution suspending a
compound containing adsorbed water or a salt containing
crystallization water, such as magnesium chloride hydrate, copper
sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate,
and cerous chloride hydrate, to make the adsorbed water or the
crystallization water react with the organoaluminum compound.
[0257] (2) A method in which water, ice, or water vapor is directly
applied to an organoaluminum compound such as a trialkylaluminum in
a medium such as benzene, toluene, ethyl ether, and
tetrahydrofuran.
[0258] (3) A method in which an organo-tin oxide such as
dimethyltin oxide and dibutyltin oxide is made react with an
organoaluminum compound such as a trialkylaluminum in a medium,
such as decane, benzene, and toluene.
[0259] The aluminoxanes may contain a small amount of an organic
metal component. Furthermore, aluminoxane in the above recovered
aluminoxane solution may be separated by distillation from the
solvent or the non-reacted organoaluminum compound, to be dissolved
again into a solvent or suspended into a poor solvent for
aluminoxane.
[0260] Specific examples of organoaluminum compounds used for
preparing the aluminoxane include those which are the same as
organoaluminum compounds exemplified by (b-1a).
[0261] Among them, trialkylaluminums and tricycloalkylaluminums are
preferable, and trimethylaluminum and triisobutylaluminum are
particularly preferable.
[0262] The organoaluminum compounds as described above can be used
singly or in combination of the two or more kinds.
[0263] A benzene-insoluble organoaluminum oxycompound which is one
aspect of the organoaluminum oxycompound (b-2) used in this
invention is preferably a compound in which the Al component
soluble into benzene at 60.degree. C. is usually 10% or less by
mass in terms of Al atom with respect to 100% by mass of benzene,
preferably 5% or less by mass, and especially preferably 2% or less
by mass, and in other words, the organoaluminum oxycompounds are
preferably insoluble or poorly soluble into benzene.
[0264] Examples of the organoaluminum oxycompound (b-2) to be used
in the invention can include those which contain boron and are
represented by the following general formula [X]
##STR00005##
[0265] [In the formula [X], R.sup.1 represents a hydrocarbon group
having 1 to 10 carbon atoms, and substituents from R.sup.2 to
R.sup.5 may be the same or different from each other and represent
a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to
10 carbon atoms.]
[0266] Organoaluminum oxycompounds containing boron, represented by
the above general formula [X] can be produced by reacting an
alkylboronic acid represented by the following general formula
[XI], with an organoaluminum compound in an inert solvent under an
inert gas atmosphere at a temperature within the range from
-80.degree. C. to room temperature for 1 minute to 24 hours.
R1-B(OH).sub.2 [XI]
[0267] (In the formula [XI], R.sup.1 represents the same group as
R.sup.1 in the above general formula [X].)
[0268] Specific examples of the alkylboronic acid represented by
the above general formula [XI] include methylboronic acid,
ethylboronic acid, isopropylboronic acid, n-propylboronic acid,
n-butylboronic acid, isobutylboronic acid, n-hexyl boronic acid,
cyclohexylboronic acid, phenylboronic acid,
3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and
3,5-bis(trifluoromethyl)phenylboronic acid, and the like.
[0269] Among them, methylboronic acid, n-butylboronic acid,
isobutylboronic acid, 3,5-difluorophenylboronic acid, and
pentafluorophenylboronic acid are preferable. These are used singly
or in combination of the two or more kinds.
[0270] Specific examples of organoaluminum compounds to be reacted
with these alkylboronic acids include those which are the same as
an organoaluminum compound exemplified by the above compound
represented by (b-1a).
[0271] Among them, trialkylaluminums and tricycloalkylaluminums are
preferable, and trimethylaluminum, triethylaluminum, and
triisobutylaluminum are particularly preferable. These are used
singly or in combination with the two or more kinds. The above
organoaluminum oxycompound (b-2) is used singly or in combination
with the two or more kinds.
[0272] ((b-3) Compound to be Reacted with Transition Metal Compound
(A) to Form an Ion Pair)
[0273] Examples of the compound (b-3) to be reacted with a
crosslinked metallocene compound (A) used in this invention, to
form an ion pair (hereinafter referred to as "ionized ionic
compounds") includes Lewis acids, ionic compounds, borane
compounds, and carborane compounds described in, for example, JP
H1-501950 A, JP H1-502036 A, JP H3-179005 A, JP H3-179006 A, JP
H3-207703 A, JP H3-207704 A, U.S. Pat. No. 5,321,106, and the like.
Further, they can include heteropolycompounds and isopolycompounds.
The ionized ionic compound (b-3) is used singly or in combination
with the two or more kinds.
[0274] Specific examples of the Lewis acids includes compounds
represented by BR3 (R is fluorine or a phenyl group which may have
a substituent, such as fluorine, methyl, and trifluoromethyl
groups), and includes, for example, trifluoroboron, triphenylboron,
tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron,
tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron,
tris(3,5-dimethylphenyl)boron.
[0275] Examples of the ionic compound include, for example,
compounds represented by following general formula [XII],
##STR00006##
[0276] (In the formula [XII], examples of R.sup.1+ include H.sup.+,
carbonium cations, oxonium cations, ammonium cations, phosphonium
cations, cycloheptyltrienyl cations, and ferrocenium cations having
a transition metal. Substituents from R.sup.2 to R.sup.5 may be the
same or different from each other, and are an organic group,
preferably an aryl or substituted aryl group.)
[0277] Specific examples of the carbonium cation include
trisubstituted carbonium cations such as triphenyl carbonium
cation, tri(methylphenyl)carbonium cation,
tri(dimethylphenyl)carbonium cation, and the like.
[0278] Specific examples of the ammonium cations include
trialkylammonium cations, such as trimethylammonium cation,
triethylammonium cation, tripropylammonium cation, tributylammonium
cation, and tri(n-butyl)ammonium cation;
[0279] N,N-dialkylanilinium cations, such as N,N-dimethylanilinium
cation, N,N-diethylanilinium cation, and
N,N,2,4,6-pentamethylanilinium cation; and
[0280] dialkylammonium cations, such as di(isopropyl)ammonium
cation and dicyclohexyl ammonium cation.
[0281] Specific examples of the phosphonium cation include
triarylphosphonium cations, such as triphenylsulfonium cation,
tri(methylphenyl)phosphonium cation, and
tri(dimethylphenyl)phosphonium cation.
[0282] Examples of R.sup.1+ are preferably carbonium cations or
ammonium cations, and triphenylcarbonium cation,
N,N-dimethylanilinium cation, and N,N-diethylanilinium cation are
particularly preferable.
[0283] Examples of the ionic compound can also include, for
example, trialkyl-substituted ammonium salts, N,N-dialkylanilinium
salts, dialkylammonium salts, and triarylphosphonium salts.
[0284] Specific examples of the trialkyl-substituted ammonium salts
include triethylammonium tetra(phenyl)boron, tripropylammonium
tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron,
trimethylammonium tetra(p-tolyl)boron, trimethylammonium
tetra(o-tolyl)boron, tri(n-butyl)ammonium
tetra(pentafluorophenyl)boron, tripropylammonium
tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium
tetra(N,N-dimethylphenyl)boron, tri(n-butyl)ammonium
tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium
tetra(3,5-ditrifluoromethylphenyl)boron, tri(n-butyl)ammonium
tetra(o-tolyl)boron, and the like.
[0285] Specific examples of the N, N-dialkylanilinium salts include
N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium
tetra(phenyl)boron, N,N,2,4,6-pentamethylanilinium
tetra(phenyl)boron, and the like.
[0286] Specific examples of the dialkylammonium salts include
di(1-propyl)ammonium tetra(pentafluorophenyl)boron,
dicyclohexylammonium tetra(phenyl)boron, and the like.
[0287] Examples of the ionic compounds also can include
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium
pentaphenylcyclopentadienyl complex, N,N-diethylanilinium
pentaphenylcyclopentadienyl complex, boron compounds represented by
the following general formula [XIII] or [XIV], and the like. In the
formulae, Et represents an ethyl group.
##STR00007##
[0288] Specific examples of the borane compounds include:
decaborane; anionic salts, such as
bis[tri(n-butyl)ammonium]nonaborate,
bis[tri(n-butyl)ammonium]decaborate,
bis[tri(n-butyl)ammonium]undecaborate,
bis[tri(n-butyl)ammonium]dodecaborate,
bis[tri(n-butyl)ammonium]decachlorodecaborate, and
bis[tri(n-butyl)ammonium]dodecachlorododecaborate; salts of metal
borane anion, such as tri(n-butyl)ammonium
bis(dodecahydridedodecaborate)cobaltate (III),
bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate
(III), and the like.
[0289] Specific examples of the carborane compounds include anionic
salts, such as 4-carbanonaborane, 1,3-dicarbanonaborane,
6,9-dicarbadecaborane,
dodecahydride-1-phenyl-1,3-dicarbanonaborane,
dodecahydride-1-methyl-1,3-dicarbanonaborane,
undecahydride-1,3-dimethyl-1,3-dicarbanonaborane,
7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane,
undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,
dodecahydride-11-methyl-2,7-dicarbaundecaborane,
tri(n-butyl)ammonium 1-carbadecaborate,
tri(n-butyl)ammonium-1-carbaundecaborate,
tri(n-butyl)ammonium-1-carbadodecaborate,
tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,
tri(n-butyl)ammonium bromo-1-carbadodecaborate,
tri(n-butyl)ammonium-6-carbadecaborate,
tri(n-butyl)ammonium-7-carbaundecaborate,
tri(n-butyl)ammonium-7,8-dicarbaundecaborate,
tri(n-butyl)ammonium-2,9-dicarbaundecaborate, tri(n-butyl)ammonium
dodecahydride-8-methyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium
undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, and
tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
and salts of metal carborane anion, such as tri(n-butyl)ammonium
bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III),
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)ferrate (III),
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)cobaltate (III),
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)nickelate (III),
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)cuprate (III),
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)aurate (III),
tri(n-butyl)ammonium
bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate (III),
tri(n-butyl)ammonium
bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate
(III), tri(n-butyl)ammonium
bis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate (III),
tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate
(III),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)man-
ganate (IV),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate
(III),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nic-
kelate (IV), and the like.
[0290] The heteropolycompounds consist of an atom selected from
silicon, phosphorus, titanium, germanium, arsenic, and tin, and one
or more kinds of atoms selected from vanadium, niobium, molybdenum,
and tungsten. Specifically, those which can be used include, but
are not limited to, phosphovanadic acid, germanovanadic acid,
arsenovanadic acid, phosphoniobic acid, germanoniobic acid,
siliconomolybdic acid, phosphomolybdic acid, titanomolibdic acid,
germanomolybdic acid arsenomolybic acid, tin molybdic acid,
phosphotungstic acid, germanotungstic acid, tin tungstic acid,
phosphomolybdovanadic acid, phosphotungstovanadic acid,
germanotungstovanadic acid, phosphomolybdotungsto vanadic acid,
germanomolybdotungstovanadic acid, phosphomolybdotungstic acid,
phosphomolybdoniobic acid, and salts of these acids, for example,
salts with Group 1 or Group 2 metals, specifically, with lithium,
sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium,
strontium, and barium, and organic salts such as triphenylethyl
salt.
[0291] Among the ionized ionic compounds (b-3), the above ionic
compounds are preferable, and especially triphenylcarbenium
tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate are more preferable. The ionized
ionic compounds (b-3) are used singly or in combination of the two
or more kinds.
[0292] In the invention, when a metallocene catalyst containing the
metallocene compound (a) represented by the above general formula
[A1], an organometallic compound (b-1) such as triisobutylaluminum,
an organoaluminum oxycompound (b-2) such as methylaluminoxane, and
an ionized ionic compound (b-3) such as triphenylcarbenium
tetrakis(pentafluorophenyl) borate is used as a catalyst, it can
exhibit very high polymerization activity in the production of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0293] The metallocene catalyst used for this invention can utilize
the above metallocene compound (a) and at least one kind of
compound (b) selected from the organometallic compound (b-1), the
organoaluminum oxycompound (b-2), and the ionized ionic compound
(b-3), and as necessary, it can also utilize a carrier (c).
[0294] ((C) Carrier)
[0295] The carrier (c) used as necessary in this invention
(microparticulate carrier) is an inorganic or organic compound,
which is a granular or microparticulate solid.
[0296] Examples of the inorganic compound are preferably porous
oxides, inorganic halides, clays, clay minerals, or
ion-exchangeable layered compounds.
[0297] Specific examples of the porous oxides which can be used
include SiO.sub.2, Al.sub.2O.sub.3, MgO, ZrO, TiO.sub.2,
B.sub.2O.sub.3, CaO, ZnO, BaO, ThO.sub.2, and the like, or
composites or mixtures containing any of them, for example, natural
or synthesized zeolite, SiO.sub.2--MgO, SiO.sub.2--Al.sub.2O.sub.3,
SiO.sub.2--TiO.sub.2, SiO.sub.2--V.sub.2O.sub.5,
SiO.sub.2--Cr.sub.2O.sub.3, SiO.sub.2--TiO.sub.2--MgO, and the
like.
[0298] Among them, those mainly composed of SiO.sub.2 and/or
Al.sub.2O.sub.3 are preferable. Although these porous oxides are
different in nature depending on their kinds and production
methods, the carrier preferably used in this invention desirably
has a particle diameter within a range from 10 to 300 .mu.m,
preferably from 20 to 200 .mu.m, a specific surface area within a
range from 50 to 1,000 m.sup.2/g, preferably 100 to 700 m.sup.2/g,
and a pore volume within a range from 0.3 to 3.0 cm.sup.3/g. Such a
carrier is used, as necessary, after calcination at a temperature
with in a range from 100 to 1,000.degree. C., preferably from 150
to 700.degree. C.
[0299] Examples of the inorganic halides to be used are MgCl.sub.2,
MgBr.sub.2, MnCl.sub.2, MnBr.sub.2, and the like. The inorganic
halides may be used as-is, or after trituration by ball milling or
vibration milling. Alternatively, they can also be used in a
microparticulate form which is obtained by precipitating, using a
precipitating agent, inorganic halide dissolved into a solvent such
as alcohol.
[0300] The clays to be used in this invention are usually composed
mainly of clay minerals. The ion-exchangeable layered compounds to
be used in this invention are compounds which have a structure in
which planes formed by, for example, ionic bonds are piled in
parallel on each other by a weak bonding force, and are compounds
containing exchangeable ions. Most clay minerals are
ion-exchangeable layered compounds. These clays, clay minerals, and
ion-exchangeable layered compounds are not limited to natural
materials, and synthesized ones can also be used.
[0301] The clays, clay minerals, and ion-exchangeable layered
compounds can be exemplified by clays, clay minerals, or ionic
crystal compounds having a layered crystalline structure, such as
the hexagonal close-packed structure, the antimony structure, the
CdCl.sub.2 structure, and the CdI.sub.2 structure. Examples of the
clays and clay minerals include kaolin, bentonite, kibushi clay,
gairome clay, allophane, hisingerite, pyrophyllite, mica group,
montmorilonite group, vermiculite, chlorite group, palygorskite,
kaolinite, nakhlite, dickite, halloysite, and the like, and
examples of the ion-exchangeable layered compound include
crystalline acidic salts of multivalent metal, such as
.alpha.-Zr(HAsO.sub.4).sub.2.H.sub.2O, .alpha.-Zr(HPO.sub.4).sub.2,
.alpha.-Zr(KPO.sub.4).sub.2.3H.sub.2O, .alpha.-Ti(HPO.sub.4).sub.2,
.alpha.-Ti(HAsO.sub.4).sub.2.H.sub.2O,
.alpha.-Sn(HPO.sub.4).sub.2.H2O, .gamma.-Zr(HPO.sub.4).sub.2,
.gamma.-Ti(HPO.sub.4).sub.2,
.gamma.-Ti(NH.sub.4PO.sub.4).sub.2.H.sub.2O, and the like.
[0302] Such clays and clay minerals, or ion-exchangeable layered
compounds have a pore volume preferably of 0.1 cc/g or more, and
particularly preferably of from 0.3 to 5 cc/g, as measured for
pores of 20 .ANG. or more in radius by using a mercury intrusion
method. The pore volume is measured for pores of 20 to 30,000 .ANG.
in a radius by a mercury intrusion method using a mercury
porosimeter.
[0303] When a carrier is used which has a pore volume of less than
0.1 cc/g as measured for pores of 20 .ANG. or more in radius, it
tends to be difficult to yield high polymerization activity.
[0304] Clay and clay mineral used in this invention are also
preferably chemically treated. Any chemical treatment can be used
such as a treatment for removing impurity attached to the surface
of the materials and a treatment affecting the crystalline
structure of the clay. Specific examples of the chemical treatment
include acid treatments, basic treatments, treatments with salts,
and treatments with organics. The acid treatments not only remove
impurities on the surface of the materials, but also increase their
surface area by eluting cations, such as Al, Fe, and Mg. The basic
treatments destroy the crystalline structure of the clay, resulting
in a change in its structure. The treatments with salts or organics
can create ionic complexes, molecular composites, organic
derivatives, and the like, to change the surface area or the
interlayer distance of the materials.
[0305] Ion-exchangeable layered compounds to be used in this
invention may be those having an increased interlayer distance
owing to the replacement of exchangeable ions between the layers
with other bulkier ions by using their ion-exchangeability. Such
bulky ions play a role of poles supporting the layered structure
and are usually called "pillars." Inserting another substance
between the layers of a layered compound is called "intercalation."
Examples of the intercalated guest compound include cationic
inorganic compounds such as TiCl.sub.4 and ZrCl.sub.4, metal
alkoxides, such as Ti(OR).sub.4, Zr(OR).sub.4, PO(OR).sub.3, and
B(OR).sub.3 (R is, for example, a hydrocarbon group), metal
hydroxide ions, such as [Al.sub.13O.sub.4(OH).sub.24].sup.7+,
[Zr.sub.4(OH).sub.14].sup.2+, and
[Fe.sub.3O(OCOCH.sub.3).sub.6].sup.+, and the like. These compounds
are used singly or in combination of the two or more kinds. These
compounds can be intercalated in the presence of polymers obtained
through hydrolysis of metal alkoxides, such as Si(OR).sub.4,
Al(OR).sub.3, and Ge(OR).sub.4 (R is, for example, a hydrocarbon
group), colloidal inorganic compounds such as SiO.sub.2, and the
like. Examples of the pillars include an oxide produced by thermal
dehydration of the above intercalated metal hydroxide ion.
[0306] The clay, clay mineral, and ion-exchangeable layered
compound to be used in this invention can be used as-is or after
treated by, for example, ball milling or sieving. They can also be
used after fresh adsorption of water or thermal dehydration.
Further, they can be used singly or in combination of the two or
more kinds.
[0307] Among them, preferable are clays or clay minerals, and
particularly preferable are montmorilonite, vermiculite, hectorite,
taeniolite, and synthesized mica.
[0308] Examples of the organic compound include granular or
microparticulate solids ranging from 10 to 300 .mu.m in particle
diameter. Specifically, they can be exemplified by polymers or
copolymers mainly composed of an .alpha.-olefin having 2 to 14
carbon atoms, such as ethylene, propylene, 1-butene, and
4-methyl-1-pentene, polymers or copolymers mainly composed of
vinylcyclohexane or styrene, and modified products thereof.
[0309] The metallocene catalyst to be used in this invention
contains not only the metallocene compound (a), at least one kind
of compound (b) selected from the organometallic compound (b-1),
the organoaluminum oxycompound (b-2), the ionized ionic compound
(b-3), and the carrier (c) used as necessary, but also the
following specific organic compound component (d), as
necessary.
[0310] ((d) Organic Compound Component)
[0311] In this invention, the organic compound component (d) is
used, as necessary, in order to improve polymerization performance
and the physical properties of the produced polymer. Examples of
such organic compound include, but are not limited to, alcohols,
phenol compounds, carboxylic acids, phosphorus compounds, and
sulfonate salts.
[0312] (Method for Producing Ethylene/.alpha.-Olefin/Non-Conjugated
Polyene Copolymer)
[0313] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
according to this invention can be produced by copolymerizing
monomers consisting of ethylene, .alpha.-olefin, and a
non-conjugated polyene.
[0314] When such monomers are copolymerized, methods of how to use
respective components composing the above polymerization catalyst
and the order of adding the components are arbitrarily selected,
and some exemplary methods are given below:
[0315] (1) A method in which the metallocene compound (a) alone is
added to a polymerizer.
[0316] (2) A method in which the metallocene compound (a) and the
compound (b) are added to the polymerizer in an arbitrary
order.
[0317] (3) A method in which a catalyst component including the
carrier (c) and the metallocene compound (a) supported on the
carrier, and the compound (b) are added to the polymerizer in an
arbitrary order.
[0318] (4) A method in which a catalyst component including the
carrier (c) and the compound (b) supported on the carrier, and the
metallocene compound (a) are added to the polymerizer in an
arbitrary order.
[0319] (5) A method in which a catalyst component including the
carrier (c) and metallocene compound (a) and the compound (b) both
supported on the carrier is added to the polymerizer.
[0320] In each of the above methods (2) to (5), at least two of the
metallocene compound (a), the compound (b), and the carrier (c) may
be contacted with each other in advance.
[0321] In each of the above methods (4) and (5) in which the
compound (b) is supported on the carrier, an additional unsupported
compound (b) may be added in an arbitrary order as necessary. In
this case, the additional compound (b) may be the same as or
different from the compound (b) supported on the carrier (c).
[0322] The solid catalyst component including the above carrier (c)
and the metallocene compound (a) supported on the carrier and the
solid catalyst component including the carrier (c) and the
metallocene compound (a) and the compound (b) both supported on the
carrier may be prepolymerized with olefin, and an additional
catalyst component may be supported on the prepolymerized solid
catalyst component.
[0323] In the invention, the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer can be suitably obtained by copolymerizing
monomers in the presence of the metallocene catalyst as described
above.
[0324] When the olefin is polymerized by using the metallocene
catalyst as described above, the metallocene compound (a) is used
usually in an amount with in a range from 10.sup.-12 to 10.sup.-2
mol, preferably from 10.sup.-10 to 10.sup.-8 mol per one liter of
the reaction volume.
[0325] The compound (b-1) is used in an amount such that the molar
ratio of the compound (b-1) to all atoms of the transition metal
(M) in the metallocene compound (a), represented by [(b-1)/M], is
usually within a range from 0.01 to 50,000, preferably from 0.05 to
10,000.
[0326] The compound (b-2) is used in an amount such that the molar
ratio of aluminum atoms of the compound (b-2) to all atoms of the
transition metal (M) in the metallocene compound (a), represented
by [(b-2)/M], is usually within a range from 10 to 50,000,
preferably from 20 to 10,000.
[0327] The compound (b-3) is used in an amount such that the molar
ratio of the compound (b-3) to atoms of the transition metal (M) in
the metallocene compound (a), represented by [(b-3)/M], is usually
within a range from 1 to 20, preferably 1 from 15.
[0328] In this invention, the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer can be
produced in either liquid phase polymerization methods such as
solution (dissolution) polymerization, suspension polymerization,
or vapor phase polymerization methods, and the methods preferably
include, but are not especially limited to, the following steps of
obtaining a polymerization-reaction solution.
[0329] The step of obtaining a polymerization-reaction solution is
a step to obtain a polymerization-reaction solution of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer by
polymerizing monomers consisting of ethylene, an .alpha.-olefin,
and a non-conjugated polyene by using an aliphatic hydrocarbon as a
polymerization solvent, in the presence of a metallocene catalyst
according to this invention, the metallocene catalyst containing a
transition metal compound wherein R.sup.13 and R.sup.14 bonding to
Y.sup.1 in the aforementioned general formula [A1] are preferably a
phenyl group, or a phenyl group substituted by an alkyl or halogen
group, and R.sup.7 and R.sup.10 preferably contain an alkyl
substituent.
[0330] When the concentration of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer in the
polymerization solvent exceeds the above range, the viscosity of
the polymerization solution too high to be stirred uniformly may
cause a difficulty in the polymerization reaction.
[0331] Examples of the polymerization solvent include aliphatic
hydrocarbons and aromatic hydrocarbons. Specific examples thereof
include aliphatic hydrocarbons, such as propane, butane, pentane,
hexane, heptane, octane, decane, dodecane, and kerosene, alicyclic
hydrocarbons, such as cyclopentane, cyclohexane, and methyl
cyclopentane, aromatic hydrocarbons, such as benzene, toluene, and
xylene, halogenated hydrocarbons, such as ethylene chloride,
chlorobenzene, and dicloromethane, and they can be used singly or
in combination of the two or more kinds. Olefins themselves can
also be used as a solvent. Among them, hexane is preferable from
the viewpoint of the separation and purification of the obtained
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0332] Polymerization temperature is usually within a range from
-50 to +200.degree. C., preferably from 0 to +200.degree. C., more
preferably from +80 to +200.degree. C., and a higher temperature
(+80.degree. C. or more) is preferable from the viewpoint of
catalyst activity, copolymerization ability, and productivity,
although depending on a molecular weight to be achieved and the
polymerization activity of a metallocene catalyst system to be
used.
[0333] Polymerization pressure is generally within a range from
atmospheric pressure to 10 MPa gauge pressure, preferably from
atmospheric pressure to 5 MPa gauge pressure, and polymerization
reaction can be carried out by any one of batchwise,
semi-continuous, and continuous methods. The polymerization can
also be carried out in two or more steps under different reaction
conditions. In this invention, it is preferable to adopt, among
them, a method of carrying out copolymerization by feeding monomers
continuously into a reactor.
[0334] Reaction time (average residence time in the case that
copolymerization is carried out continuously) varies depending on
conditions such as catalyst concentration and polymerization
temperature, but it is usually within a range from 0.5 minutes to 5
hours, preferably 5 minutes to 3 hours.
[0335] The molecular weight of the obtained
ethylene/.alpha.-olefin/non-conjugated polyene copolymer can also
be controlled by adding hydrogen in the polymerization system or by
changing the polymerization temperature. It can also be controlled
by the amount of the compound (b) to be used. Specific examples of
the compound include triisobutylaluminum, methylaluminoxane, and
diethyl zinc. When hydrogen is added, its amount is suitably with
in a range from about 0.001 to about 100 NL per 1 kg of olefin.
[0336] The charged molar ratio of ethylene to the above
.alpha.-olefin, (ethylene/.alpha.-olefin), is preferably with in a
range from 40/60 to 99.9/0.1, more preferably from 40/60 to 85/15,
still more preferably from 55/45 to 85/15, and most preferably from
55/45 to 78/22.
[0337] The charged amount of the non-conjugated polyene is usually
within a range from 0.07 to 10% by mass, preferably from 0.1% by
mass to 8.0% by mass, more preferably from 0.5% by mass to 5.0% by
mass, with respect to 100% by mass of the sum of ethylene,
.alpha.-olefin, and non-conjugated polyene (total amount of the
total charged monomers in a case in which different monomers are
used).
[0338] (Ethylene/Carboxylic Acid Copolymer)
[0339] The ethylene/carboxylic acid copolymer is not particularly
limited as long as it has an ethylene-derived structural unit and a
carboxylic acid-derived structural unit. The ethylene/carboxylic
acid copolymer is preferably an ethylene/unsaturated carboxylic
acid copolymer. Note that according to this invention, the
ethylene/carboxylic acid copolymer include ethylene/carboxylic
anhydride copolymer. In this case, the ethylene/carboxylic acid
copolymer is not particularly limited as long as it has an
ethylene-derived structural unit and a carboxylic anhydride-derived
structural unit.
[0340] The melt flow rate (MFR) (190.degree. C., a load of 2160 g,
JIS K7210 (1999)) of the ethylene/carboxylic acid copolymer is not
particularly limited. However, it is preferably from 0.01 g/10
minutes to 150 g/10 minutes, more preferably from 0.1 g/10 minutes
to 100 g/10 minutes, and particularly preferably from 0.5 to 50
g/10 minutes.
[0341] The ethylene/unsaturated carboxylic acid copolymer is a
copolymer in which at least ethylene and unsaturated carboxylic
acid are copolymerized. In other words, the ethylene/unsaturated
carboxylic acid copolymer is a copolymer having a structural unit
derived from ethylene and a structural unit derived from
unsaturated carboxylic acid. Monomers other than ethylene and
unsaturated carboxylic acid may be used for the
ethylene/unsaturated carboxylic acid copolymer. In other words, the
ethylene/unsaturated carboxylic acid copolymer may have structural
units derived from monomers other than ethylene and unsaturated
carboxylic acid.
[0342] The ethylene/unsaturated carboxylic acid copolymer is
preferably at least one member selected from the group consisting
of ethylene/unsaturated carboxylic acid binary copolymers and
ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid
ester ternary copolymers.
[0343] The content of a structural unit derived from ethylene in
the ethylene/unsaturated carboxylic acid copolymer is preferably
from 60% by mass to 98% by mass, more preferably from 70% by mass
to 98% by mass, and particularly preferably from 75% by mass to 97%
by mass with respect to the total amount of the
ethylene/unsaturated carboxylic acid copolymer.
[0344] An example of unsaturated carboxylic acid is an
.alpha.-.beta., unsaturated carboxylic acid. Specific examples
thereof include unsaturated carboxylic acids or half esters having
4 to 8 carbon atoms such as acrylic acid, methacrylic acid,
ethacrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic
acid, and maleic acid monoesters (e.g., maleic acid monomethyl and
maleic acid monoethyl). Preferable examples of unsaturated
carboxylic acid include acrylic acid and methacrylic acid. In
addition, unsaturated carboxylic acid may be unsaturated carboxylic
acid anhydride. Examples of unsaturated carboxylic acid anhydride
include maleic anhydride, phthalic anhydride, and acetic anhydride.
Of these, maleic anhydride is preferable.
[0345] The content of a structural unit derived from unsaturated
carboxylic acid in the ethylene/unsaturated carboxylic acid
copolymer is preferably from 2% by mass to 25% by mass and more
preferably from 2% by mass to 20% by mass with respect to the total
amount of the ethylene/unsaturated carboxylic acid copolymer.
[0346] Examples of unsaturated carboxylic acid ester include
.alpha.-.beta., unsaturated carboxylic acid esters, which are
preferably .alpha.-.beta., unsaturated carboxylic acid alkylesters
having an alkyl moiety with 1 to 8 carbon atoms, and more
preferably acrylic acid methyl, acrylic acid ethyl, acrylic acid
isobutyl, acrylic acid n-butyl, methacrylic acid ethyl, ethyl
methacrylate, isobutyl methacrylate, and n-butyl methacrylate.
[0347] In a case in which the ethylene/unsaturated carboxylic acid
copolymer contains a structural unit derived from unsaturated
carboxylic acid ester, the content of unsaturated carboxylic acid
ester is preferably from more than 0% by mass to 25% by mass, more
preferably from 2% by mass to 25% by mass, and particularly
preferably from 2% by mass to 20% by mass with respect to the total
amount of the ethylene/unsaturated carboxylic acid copolymer.
[0348] Examples of different monomers (monomers other than
ethylene, unsaturated carboxylic acid, and unsaturated carboxylic
acid ester) which can be copolymerized to form an
ethylene/unsaturated carboxylic acid copolymer include carbon
monoxide, glycidyl acrylate, and glycidyl methacrylate.
[0349] In a case in which the ethylene/unsaturated carboxylic acid
copolymer contains structural units derived from the
above-described different monomers, the content of structural units
derived from the different monomers is preferably 20% by mass or
less, more preferably 10% by mass or less, and still more
preferably 5% by mass or less with respect to the total amount of
the ethylene/unsaturated carboxylic acid copolymer.
[0350] Specific examples of an ethylene/carboxylic acid copolymer
used in this invention include an ethylene/methacrylic acid
copolymer, an ethylene/acrylic acid copolymer, and an
ethylene/maleic anhydride copolymer.
[0351] Products including commercially available products can be
used as the ethylene/unsaturated carboxylic acid copolymer without
particular limitations. A method of producing thereof may also be
any method such as a known method without particular
limitation.
[0352] (Acrylic-Type Rubber)
[0353] According to this invention, an acrylic-type rubber is a
rubber or a composite rubber formed with a polymer containing a
structural unit derived from a (metha)acrylic-type monomer. An
acrylic-type rubber is a polymer containing a structural unit
derived from a (metha)acrylic-type monomer at from 50% to 100% by
mass and also containing a structural unit derived from a different
monomer within a range of 0% to 50% by mass.
[0354] According to this invention, the term "(metha) acrylic-type
monomer" is used to mean a methacrylic monomer or an acrylic-type
monomer. The term "methacrylic monomer" used herein refers to a
monomer having one CH.sub.2.dbd.CH(CH.sub.3)--COO-- structure in
its molecule and the term "acrylic-type monomer" refers to a
monomer having one CH.sub.2.dbd.CH.sub.2--COO-- structure in its
molecule.
[0355] The term "composite rubber" refers to a rubber obtained via
stepwise polymerization rather than simple polymerization in a case
in which a polymer containing a structural unit derived from the
above-described (metha) acrylic-type monomer is polymerized using
two or more kinds of monomers.
[0356] A usual (metha)acrylic-type monomer to be used is, but is
not particularly limited to, (metha)acrylate. Specific examples
thereof include methylacrylate, ethylacrylate, n-propylacrylate,
n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tridecyl
acrylate, ethoxyethoxyethylacrylate, methoxytripropylene glycol
acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, lauryl
methacrylate, tridecyl methacrylate, and stearyl methacrylate.
These monomers may be used singly or in combination of the two or
more kinds.
[0357] Among these monomers, in terms of rubber elasticity,
modulus, mechanical strength, and oil resistance, n-butyl acrylate,
2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, tridecyl
acrylate, lauryl methacrylate, and tridecyl methacrylate are
preferable.
[0358] As described above, an acrylic-type rubber may contain a
structural unit derived from a monomer other than a
(metha)acrylic-type monomer. Examples of different monomers that
can be used include: .alpha.-olefins such as ethylene, propylene,
and 1-butene; diene-based monomers such as 1,3-butadiene, isoprene,
and chloroprene; aromatic vinyls such as styrene and
.alpha.-methylstyrene; unsaturated nitriles such as acrylonitrile
and methacrylonitrile; vinyl ethers such as methylvinyl ether and
butyl vinyl ether; halogenated vinyls such as vinyl chloride and
vinyl bromide; halogenated vinylidenes such as vinylidene chloride
and vinylidene bromide; vinyl-based monomers having a glycidyl
group such as glycidyl acrylate, glycidyl methacrylate, allyl
glycidyl ether, and ethylene glycol glycidyl ether; polyfunctional
monomers such as divinylbenzene, ethylene glycol dimethacrylate,
and 1,3-butylene glycol dimethacrylate. In addition, these
different monomers may be used singly or in combination of the two
or more kinds.
[0359] When an acrylic-type rubber is produced, a crosslinking
agent may be used. As a crosslinking agent, a monomer containing
two or more unsaturated bonds in its molecule is usually used.
[0360] In a case in which a monomer containing two or more
unsaturated bonds in its molecule is used, assuming that the mass
of a monomer to be used is 100% by mass, the monomer is used at
preferably from 0.01% to 2% by mass and more preferably from 0.05%
to 1.5% by mass.
[0361] Examples of crosslinking agents include, for example,
ethylene glycol dimethacrylate, propyleneglycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,4-butylene glycol
dimethacrylate, divinylbenzene, and polyfunctional methacyrl
group-denatured silicone. Such crosslinking agents may be used
singly or in combination of the two or more kinds.
[0362] As an acrylic-type rubber, any product such as a
commercially available product can be used without particular
limitations. A method of producing an acrylic-type rubber is not
particularly limited. However, an acrylic-type rubber can be
produced by, for example, a method of emulsion polymerization,
suspension polymerization, or the like using, as an emulsifier or
dispersion stabilizer, a variety of surfactants such as anionic
surfactants, nonionic surfactants, and cationic surfactants.
[0363] (Halogen-Containing Polymer)
[0364] The term "halogen-containing polymer" refers to a polymer
having halogen atom(s) in its molecule, which is preferably a
polymer containing a structural unit derived from a
halogen-containing monomer.
[0365] Examples of halogen atoms include a fluorine atom, a
chlorine atom, bromine atom, and an iodine atom. However, as a
halogen-containing polymer, a polymer containing a fluorine atom
which is a fluorine atom-containing polymer is preferable.
[0366] A halogen-containing polymer is preferably a rubber and more
preferably a rubber of a fluorine atom-containing polymer which is
a fluorine rubber.
[0367] Examples of a fluorine rubber include, for example:
VdF/perhal-olefin-based elastomers such as vinylidene fluoride
(VdF)/hexafluoropropylene(HFP) copolymer, VdF/tetrafluoroethylene
(TFE)/HFPcopolymer, VdF/TFE/perfluoro (alkylvinyl ether) (PAVE)
copolymer, VdF/chlorotrifluoroethylene (CTFE) copolymer;
VdF/non-perhalo-olefin-based elastomers such as a TFE/propylene/VdF
copolymer and a HFP/ethylene/VdF copolymer; perfluoro elastomers
such as a TFE/PAVE copolymer; non-perfluoro elastomers such as a
TFE/propylene copolymer and a HFP/ethylene copolymer; and
fluorosilicone rubbers.
[0368] The above-described fluoro(alkylvinyl ether) may contain a
plurality of ether bonds. Further, the molecular weight of fluorine
rubber is from 20,000 to 300,000 and preferably from 50,000 to
200,000 in terms of the number average molecular weight.
[0369] Among them, in terms of thermal resistance, oil resistance,
and chemical resistance, elastomers of a VdF/HFP copolymer, a
VdF/TFE/HFP copolymer, a VdF/TFE/PAVE copolymer, a
TFE/propylene/VdF copolymer, a HFP/ethylene/VdF copolymer, a
TFE/propylene copolymer, and a HFP/ethylene copolymer are
preferable, and elastomers of a VdF/HFP copolymer and a VdF/TFE/HFP
copolymer are particularly preferable.
[0370] In a fluorine rubber, as a structural unit containing a
crosslinkable group, a polyfunctional monomer containing a
plurality of vinyl groups or allyl groups or an iodine or
bromine-containing monomer may be copolymerized. In addition, it is
also possible to cause double bonds, which may serve as
crosslinkable sites, to be generated in a molecule of such rubber
by promoting dehydrofluorination with heat treatment or the like. A
fluorine rubber, in which olefin iodide or olefin bromide is used
as a crosslinkable unit, and which contains a structural unit
derived from olefin iodide or a structural unit derived from olefin
bromide, is particularly preferable.
[0371] In addition, the content of crosslinkable sites (for
example, the content of a structural unit derived from olefin
bromide when olefin bromide is used as a crosslinkable unit) in a
fluorine rubber is preferably from 0.05 to 5 mol %, more preferably
from 0.15 to 3 mol %, and particularly preferably from 0.25 to 2
mol %. When there are fewer crosslinkable sites than the above,
sealing performance or bonding strength becomes insufficient. When
there are more crosslinkable sites than the above, elongation or
flexibility is reduced, which results in loss of rubber
elasticity.
[0372] Next, the above-described layers (1) to (4) will be
described.
[0373] (Layer (1))
[0374] The layer (1) is a layer prepared using an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0375] It is possible to prepare the layer (1) using at least an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer. In
general, it is a layer prepared using not only an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer but also
other components as starting materials. The layer (1) is usually a
layer prepared by crosslinking using an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer. Examples
of components other than the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer include: (B) an organic peroxide; (C) carbon
black; (D) an antioxidant; (E) a softening agent; (F) a metal
oxide; (G) a crosslinking aid; (H) an onium salt; (I) an inorganic
compound containing oxygen and at least one element selected from
Group 2 elements and Group 13 elements; and (J) other
components.
[0376] ((B) Organic Peroxide)
[0377] Any organic peroxide that can act as a crosslinking agent
for the ethylene/.alpha.-olefin/non-conjugated polyene copolymer
can be suitably used as the organic peroxide (B).
[0378] Specific examples of the organic peroxide (B) include
dicumyl peroxide, di-tert-butyl peroxide,
2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyis-
opropyl)benzene,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,
n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide,
p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate,
diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, and
the like.
[0379] The organic peroxide (B) can be used singly or in
combination of two or more kinds.
[0380] The organic peroxide (B) is used preferably in an amount
with in a range of 0.1 to 5 parts by mass, preferably 0.5 to 5
parts by mass, and more preferably 0.5 to 4 parts by mass, with
respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer. The
compounded amount of the organic peroxide (B) within the above
range is suitable because crosslinked shaped articles have no bloom
on the surface thereof and the rubber shaped articles exhibit
excellent crosslinking characteristics.
[0381] ((C) Carbon Black)
[0382] Examples of the carbon black (C) include various carbon
blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT, and
surface treated carbon blacks which are these carbon blacks
surface-treated with an agent such as a silane coupling agent.
[0383] The compounded amount of the carbon black (C) may be 10 to
300 parts by mass, preferably 10 to 200 parts by mass, more
preferably 10 to 100 parts by mass, with respect to 100 parts by
mass of the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer.
[0384] When the content of carbon black (C) is within the above
range, it is preferable because it can provide a layered product
having improved mechanical properties such as tensile strength and
abrasion resistance and increase the hardness thereof without
impairing other physical properties thereof.
[0385] ((D) Antioxidant)
[0386] When an antioxidant (D) is contained, it can prolong the
life-time of shaped article. Antioxidants (D) which may be used are
conventionally well-known antioxidants, for example, amine-based
antioxidants, phenol-based antioxidants, and sulfur-based
antioxidants.
[0387] Specific examples of the antioxidant (D) include
aromatic-secondary-amine-based antioxidants such as
phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine, and
4,4'-bis (.alpha.,.alpha.-dimethylbenzyl)diphenylamine (also known
as "4,4'-dicumyl-diphenylamine"), amine-based antioxidants such as
2,2,4-trimethyl-1,2-dihydroquinoline polymer, phenol-based
antioxidants such as dibutylhydroxytoluene and
tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane;
thioether antioxidants such as
bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide;
dithiocarbamate-based antioxidants such as nickel
dibutyldithiocarbamate; zinc salts of 2-mercaptobenzoylimidazole
and 2-mercaptobenzoimidazole; sulfur-based antioxidants such as
dilaurylthiodipropionate and distearylthiodipropionate, and the
like.
[0388] These antioxidants (D) can be used singly or in combination
of two or more kinds.
[0389] The compounded amount of the antioxidants (D) is within a
range of 0.5 to 5.0 parts by mass, and preferably 0.5 to 4.5 parts
by mass, more preferably 0.5 to 4.0 parts by mass, with respect to
100 parts by mass of the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer. When the compounded amount is within the above
range, it is preferable because the layered product has excellent
heat aging resistance.
[0390] ((E) Softening Agent)
[0391] Agents known as components conventionally compounded in
rubbers, such as softening agents and processing aids, can be
widely used as the softening agent (E).
[0392] Specific examples of the agent include:
[0393] petroleum-based softening agents such as paraffin-based
processed oils, naphthene-based processed oils, and aromatic
processed oils;
[0394] softening materials based on synthesized oils;
[0395] cooligomer of ethylene and .alpha.-olefin;
[0396] paraffin wax;
[0397] liquid paraffin;
[0398] white oil;
[0399] petrolatum;
[0400] softening agents based on coal tar such as coal tar and coal
tar pitch;
[0401] softening agents based on vegetable oils, such as castor
oil, cotton oil, linseed oil, canola oil, coconut oil, palm oil,
soya oil, groundnut oil, Japan wax, rosin, pine oil, dipentene,
pine tar, and tall oil;
[0402] substitutes (factices), such as black substitute, white
substitute, and candy substitute;
[0403] waxes, such as beeswax, carnauba wax, and lanolin;
[0404] fatty acids, fatty acid salts and esters, such as ricinoleic
acid, palmitic acid, stearic acid, linoleic acid, lauric acid,
myristic acid, barium stearate, calcium stearate, magnesium
stearate, zinc stearate, and zinc laurate;
[0405] ester-based plasticizers, such as dioctyl phthalate, dioctyl
adipate, and dioctyl sebacate;
[0406] coumarone-indene resin;
[0407] phenol-formaldehyde resin;
[0408] terpene-phenol resin;
[0409] polyterpene resin;
[0410] petroleum-based hydrocarbon resins, such as synthesized
polyterpene resins, aromatic hydrocarbon resins, aliphatic
hydrocarbon resins, aliphatic ring hydrocarbon resins,
aliphatic/alicyclic petroleum resins, aliphatic/aromatic petroleum
resins, hydrogenated modified alicyclic hydrocarbon resins,
hydrogenated hydrocarbon resins, liquid polybutene, liquid
polybutadiene, atactic polypropylene, and the like.
[0411] Among them, fatty acid, petroleum-based softening agents,
phenol-formaldehyde resin, petroleum-based hydrocarbon resins are
preferable, fatty acid, petroleum-based softening agents, and
petroleum-based hydrocarbon resins are more preferable, and fatty
acid and petroleum-based softening agents are particularly
preferable.
[0412] Among the petroleum-based softening agents, preferable are
petroleum-based processed oils, among which paraffin-based
processed oils, naphthene-based processed oils, aromatic processed
oils are more preferable, and paraffin-based processed oils are
particularly preferable. Among the petroleum-based hydrocarbon
resins, aliphatic ring hydrocarbon resins are preferable. Among
these softening agents, paraffin-based processed oils are
particularly preferable.
[0413] These softening agents can be used singly or in combination
of the two or more kinds.
[0414] The compounded amount of the softening agent (E) is not
particularly limited, but it is usually less than 200 parts by
mass, and is preferably from 0 to 100 parts by mass, more
preferably from 0 to 80 parts by mass, still more preferably from 0
to 70 parts by mass, and particularly preferably from 0 to 60 parts
by mass with respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0415] (F) Metal Oxide
[0416] Metal oxides can be appropriately selected depending on
applications of the layered product and can be used singly or in
combination of two or more kinds. Specific examples of metal oxides
include zinc flower (for example, META-Z102) (trade name: zinc
oxide manufactured by Inoue Calcium Corporation or the like) and
magnesium oxide. The compounded amount thereof is usually from 0.5
to 20 parts by mass, preferably from 0.5 to 15 parts by mass, more
preferably from 0.5 to 10 parts by mass, still more preferably from
0.5 to 5 parts by mass with respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0417] ((G) Crosslinking Aid)
[0418] Examples of the crosslinking aid (G) include: sulfur;
quinonedioxime compounds such as p-quinonedioxime; polyfunctional
monomers, such as (meth) acrylate compounds, such as
trimethylolpropane triacrylate and polyethylene glycol
dimethacrylate; allyl compounds such as diallylphthalate and
triallyl cyanurate; maleimide compounds such as m-phenylene
bismaleimide; divinylbenzene, and the like. The crosslinking aid
(G) may be used singly or in combination of two or more kinds.
[0419] The compounded amount of the crosslinking aid (G) is not
particularly limited, but it is usually 0 to 4.0 parts by mass, and
is preferably 0 to 3.5 parts by mass, more preferably 0 to 3.0
parts by mass, still more preferably 0.1 to 3.0 parts by mass, with
respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer. It is
also desirable that the compounded amount of the crosslinking aid
(G) is preferably with in a range from 0.5 to 2 mols, more
preferably approximately equimolar, with respect to 1 mol of the
organic peroxide (B).
[0420] ((H) Onium Salt)
[0421] Examples of the onium salt (H) include, for example,
quaternary ammonium salts, quaternary phosphonium salts, oxonium
salts, sulfonium salts, cyclic amine, and monofunctional amine
compounds. Among them, quaternary ammonium salts and quaternary
phosphonium salts are preferable.
[0422] Such onium salts (H) may be used singly or in combination of
the two or more kinds.
[0423] Examples of quaternary ammonium salts include, but are not
particularly limited to, dialkyl(C14-18) dimethylammonium chloride,
1,8-diazabicyclo[5,4,0]-7-undecenium salts,
8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride,
8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium iodide,
8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide,
8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium methyl sulfate,
8-ethyl-1,8-diazabicyclo[5,4,0]-7-undecenium bromide,
8-propyl-1,8-diazabicyclo[5,4,0]-7-undecenium bromide,
8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride,
8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide,
8-eicosyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride,
8-tetracosyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride,
8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride (hereinafter
referred to as "DBU-B"),
8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide,
8-phenethyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, and
8-(3-phenyl propyl)-1,8-diazabicyclo[5,4,0]-7-undecenium chloride.
Among them, dialkyl(C14-18) dimethylammonium chloride is
preferable.
[0424] Examples of quaternary phosphonium salts include, but are
not particularly limited to, for example, tetrabutyl phosphonium
chloride, benzyltriphenylphosphonium chloride (hereinafter referred
to as "BTPPC"), benzyltrimethylphosphonium chloride,
benzyltributylphosphonium chloride, tributylallyl phosphonium
chloride, tributyl-2-methoxy propylphosphonium chloride, and
benzylphenyl (dimethylamino) phosphonium chloride. Among them, in
terms of vulcanization performance and physical properties of
vulcanized products, benzyltriphenylphosphonium chloride (BTPPC) is
preferable.
[0425] It is also possible to use a solid solution of, a quaternary
ammonium salt, a quaternary phosphonium salt, and bisphenol AF and
a compound disclosed in JP H11-147891 A.
[0426] In addition, examples of an amine compound include, for
example, hexamethylenediaminecarbamate,
N,N'-dicinnamylidene-1,6-hexamethylenediamine, and 4,4'-bis(amino
cyclohexyl) methanecarbamate. Among them,
N,N'-dicinnamylidene-1,6-hexamethylenediamine is preferable.
[0427] As the onium salt (H), a commercially available product may
be used. For example, "LIPOQUAD 2HT FLAKE" (manufactured by Lion
Specialty Chemicals Co., Ltd., dialkyl (C14-18) dimethylammonium
chloride, also referred to as "LIPOQUAD 2HTF" in this invention)
can be used.
[0428] The compounded amount of the onium salt (H) to be used is
preferably 0.2 parts by mass or more, more preferably from 0.2
parts by mass to 10 parts by mass, and still more preferably from
0.5 parts by mass to 8 parts by mass with respect to 100 parts by
mass of the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer. When the onium salt (H) is used in the above range with
an inorganic compound containing oxygen and at least one kind of
element selected from Group 2 elements and Group 13 elements
described in (I) below, excellent adhesiveness to the layer (4) (a
layer prepared using a halogen-containing polymer) is achieved,
which is preferable.
[0429] Although components classified as onium salts (H) are
described as other components (J), a component (H) and a compound
corresponding to the other component are classified as components
(H) in a case in which a component (H) and a component (I)
described below are used as components constituting the layer.
[0430] ((I) Inorganic Compound Containing Oxygen and at Least One
Element Selected from Group 2 Elements and Group 13 Elements)
[0431] Examples of the inorganic compound containing oxygen and at
least one element selected from Group 2 elements and Group 13
elements (I) include, but are not particularly limited to, for
example, an oxide, a hydroxide, a carbonate, and a hydrotalcite
compound at least one element selected from Group 2 elements and
Group 13 elements.
[0432] Examples of at least one element selected from Group 2
elements and Group 13 elements include, for example, at least one
element selected from Mg, Ca, Ba, and Al.
[0433] As the inorganic compound containing oxygen and at least one
element selected from Group 2 elements and Group 13 elements (I), a
commercially available product may be used. For example, "Kyowamag
150" (manufactured by Kyowa Chemical Industry Co., Ltd., magnesium
oxide) or DHT-4A (manufactured by Kyowa Chemical Industry Co.,
Ltd., hydrotalcite compound: Mg.sub.4.3Al.sub.2(OH)
1.sub.2.6CO.sub.3/mH.sub.2O) can be used.
[0434] When the inorganic compound containing oxygen and at least
one element selected from Group 2 elements and Group 13 elements
(I) is used, the compounded amount is preferably 7 parts by mass or
more and more preferably from 7 parts by mass to 100 parts by mass
with respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer. The lower
limit of the inorganic compound containing oxygen and at least one
element selected from Group 2 elements and Group 13 elements (I) is
particularly preferably 10 parts by mass or more. The upper limit
thereof is more preferably 80 parts by mass or less, still more
preferably 50 parts by mass or less, particularly preferably 40
parts by mass or less, and most preferably 35 parts by mass or
less.
[0435] Although components classified as inorganic compounds
containing oxygen at least one element selected from Group 2
elements and Group 13 elements (I) are described for the metal
oxide (F) and the other component (J), compounds corresponding to
the component (I) and the other component are classified as
components (I) in a case in which the components (H) and (I) are
used as components constituting the layer.
[0436] ((J) Additional Component)
[0437] Examples of the additional component (J) include various
additive components conventionally added to the rubber composition
such as a filler, a foaming agent, an antioxidant, a processing
aid, surfactants, and a weathering agent. A resin component other
than the ethylene/.alpha.-olefin/non-conjugated polyene copolymer
may be contained, as necessary.
[0438] Examples of the filler include inorganic fillers such as
silica, activated calcium carbonate, light calcium carbonate, heavy
calcium carbonate, fine powdered talc, talc, fine powder silicic
acid, and clay. These fillers can be in an amount of from 0 to 300
parts by mass and preferably from about 0 to 200 parts by mass with
respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer. When a
filler is used, a layered product can be obtained which has
improved mechanical properties, such as tensile strength, tear
strength, and abrasion resistance, and increased hardness without
impairing its other physical properties.
[0439] The resin composition according to this invention preferably
contains an antioxidant from the viewpoint of capability to prolong
its material life. Examples of the antioxidant include:
[0440] stabilizing agents based on aromatic secondary amines, such
as phenylnaphthylamine,
4,4'-(.alpha.,.alpha.-dimethylbenzyl)diphenylamine,
N,N'-di-2-naphthyl-p-phenylenediamine;
[0441] stabilizing agents based on phenol, such as
2,6-di-t-butyl-4-methylphenol,
tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne;
[0442] stabilizing agent based on thioether such as
bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide;
[0443] stabilizing agent based on benzoimidazole such as
2-mercaptobenzoimidazole;
[0444] stabilizing agent based on dithiocrabamates such as nickel
dibutyldithiocarbamate;
[0445] stabilizing agent based on quinoline such as a polymerized
product of 2,2,4-trimethyl-1,2-dihydroquinoline, and the like.
These may be used alone or in combination of two or more kinds.
[0446] The antioxidant can be used in an amount of, for example, 5
parts by mass or less, preferably 3 parts by mass or less, with
respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0447] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
also can appropriately contain, if necessary, various additives
that can be compounded in known rubber compositions.
[0448] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
may be mixed with a surfactant. Examples of the surfactant include
amines, such as di-n-butylamine, dicyclohexylamine,
monoethanolamine, triethanolamine, "Acting B" (manufactured by
YOSHITOMI PHARMACEUTICAL INDUSTRIES, LTD.), "Acting SL"
(manufactured by YOSHITOMI PHARMACEUTICAL INDUSTRIES, LTD.),
polyethylene glycol, diethylene glycol, polyethylene glycol,
lecithin, triallyltrimellitate, and compounds of zinc aliphatic or
aromatic carboxylate (example; "Struktol activator 73", "Struktol
IB 531", and "Struktol FA 541", manufactured by Schill+Seilacher
GmbH), "ZEONET ZP" (manufactured by ZEON CORPORATION),
octadecyltrimethylammonium bromide, synthesized hydrotalcite, and
special quaternary ammonium compounds (example; "LIPOQUAD 2HTF"
(manufactured by Lion Specialty Chemicals Co., Ltd., dialkyl
(C14-18) dimethylammonium chloride)), and the like. LIPOQUAD 2HTF
is the most preferable surfactant.
[0449] When the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer is mixed with a surfactant, the compounded amount of the
surfactant is, for example, about 0.2 to 10 parts by mass,
preferably about 0.3 to 8 parts by mass, more preferably about 0.3
to 7 parts by mass, particularly preferably about 0.5 to 7 parts by
mass, and most preferably about 1 to 6 parts by mass with respect
to 100 parts by mass of the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer. The surfactant can be appropriately selected
depending on its use, and it can be used singly or in combination
of the two or more kinds.
[0450] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
may be mixed with a pseudo-gel inhibitor. Examples of the
pseudo-gel inhibitor include, for example, "NHM-007" (manufactured
by Mitsui Chemicals, Inc.).
[0451] When the ethylene/.alpha.-olefin/non-conjugated polyene
copolymer is mixed with a pseudo-gel inhibitor, the compounded
amount thereof is within a range usually from 0.1 to 15 parts by
mass, and preferably from 0.5 to 12 parts by mass, more preferably
1.0 to 10 parts by mass, with respect to 100 parts by mass of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer.
[0452] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
may be further mixed with an additional additive, as necessary.
Examples of the additional additive include agents such as heat
stabilizers, weathering stabilizers, antistatic agents, colorants,
lubricants, and thickeners.
[0453] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
may be mixed with an additional resin component other than the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer, as
necessary. Examples of the additional resin component include, but
are not particularly limited to, polyolefin resins.
[0454] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
mixed with a polyolefin resin enables controlling the hardness of
products from the composition and decreasing its compound viscosity
at processing temperature, resulting in further improvement of its
processability. It is also preferable because it can be treated as
a thermoplastic elastomer, resulting in its easier handling
property and more choices of kneading methodology.
[0455] The polyolefin resin having a number-average molecular
weight, as measured by GPC, of 10,000 or more in terms of
polystyrene standard is suitably used.
[0456] Examples of the polyolefin resin include an .alpha.-olefin
homopolymer and an .alpha.-olefin copolymer. Examples of the
.alpha.-olefin homopolymer include polyethylene, polypropylene, and
the like, and examples of the .alpha.-olefin copolymer include a
copolymer of ethylene/.alpha.-olefin having 3 to 20 carbon atoms.
Examples of the copolymer of ethylene/.alpha.-olefin having 3 to 20
carbon atoms include ethylene-propylene rubber (EPR),
propylene-ethylene rubber (PER), ethylene-butene rubber (EBR),
ethylene-octene rubber (EOR), and the like.
[0457] Among these polyolefin resins, polyethylene,
ethylene/.alpha.-olefin copolymer, and polypropylene are
preferable.
[0458] The polyolefin resins can be used singly or in combination
of the two or more kinds.
[0459] When a polyolefin resin is added to the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer, the
content of the polyolefin resin is, for example, from 1 to 100
parts by mass, preferably from 5 to 80 parts by mass, and more
preferably from 10 to 50 parts by mass or thereabouts with respect
to 100 parts by mass of the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer.
[0460] In the above range, it is possible to control the hardness
of a layered product and decrease its compound viscosity at
processing temperature, resulting in further improvement of its
processability. It is also preferable because layered product can
be treated as a thermoplastic elastomer, resulting in its easier
handling property and more choices of kneading methodology.
[0461] (Layer (2))
[0462] The layer (2) is a layer prepared using an
ethylene/carboxylic acid copolymer.
[0463] It is possible to prepare the layer (2) using at least an
ethylene/carboxylic acid copolymer. In general, it is a layer
prepared using not only an ethylene/carboxylic acid copolymer but
also other components as starting materials. The layer (2) is
usually a layer prepared by crosslinking using an
ethylene/carboxylic acid copolymer. Examples of components other
than the ethylene/carboxylic acid copolymer include: (B) an organic
peroxide; (C) carbon black; (D) an antioxidant; (E) a softening
agent; (F) a metal oxide; (G) a crosslinking aid; (H) an onium
salt; (I) an inorganic compound containing oxygen and at least one
element selected from Group 2 elements and Group 13 elements; and
(J) other components described above for the layer (1). The amounts
of (B) to (J) in the layer (2) are specified with respect to the
amount of ethylene/.alpha.-olefin/non-conjugated polyene copolymer
for the layer (1). The amount of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer is
replaced by the amount of the ethylene/carboxylic acid
copolymer.
[0464] (Layer (3))
[0465] The layer (3) is a layer prepared using an acrylic-type
rubber.
[0466] It is possible to prepare the layer (3) using at least an
acrylic-type rubber. In general, it is a layer prepared using not
only an acrylic-type rubber but also other components as starting
materials. The layer (3) is usually a layer prepared by
crosslinking using an acrylic-type rubber. Examples of components
other than the acrylic-type rubber include: (B) an organic
peroxide; (C) carbon black; (D) an antioxidant; (E) a softening
agent; (F) a metal oxide; (G) a crosslinking aid; (H) an onium
salt; (I) an inorganic compound containing oxygen and at least one
element selected from Group 2 elements and Group 13 elements; and
(J) other components described above for the layer (1). The amounts
of (B) to (J) in the layer (3) are specified with respect to the
amount of ethylene/.alpha.-olefin/non-conjugated polyene copolymer
for the layer (1). The amount of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer is
replaced by the amount of the acrylic-type rubber.
[0467] (Layer (4))
[0468] The layer (4) is a layer prepared using a halogen-containing
polymer.
[0469] It is possible to prepare the layer (4) using at least a
halogen-containing polymer. In general, it is a layer prepared
using not only a halogen-containing polymer but also other
components as starting materials. The layer (4) is usually a layer
prepared by crosslinking using a halogen-containing polymer.
Examples of components other than the halogen-containing polymer
include: (B) an organic peroxide; (C) carbon black; (D) an
antioxidant; (E) a softening agent; (F) a metal oxide; (G) a
crosslinking aid; (H) an onium salt; (I) an inorganic compound
containing oxygen and at least one element selected from Group 2
elements and Group 13 elements; and (J) other components described
above for the layer (1). The amounts of (B) to (J) in the layer (4)
are specified with respect to the amount of
ethylene/.alpha.-olefin/non-conjugated polyene copolymer for the
layer (1). The amount of the ethylene/.alpha.-olefin/non-conjugated
polyene copolymer is replaced by the amount of the
halogen-containing polymer.
[0470] As a method of crosslinking a halogen-containing polymer
such as a fluorine rubber, polyol crosslinking, peroxide
crosslinking, and amine crosslinking are known in general. Among
them, at present, amine crosslinking is unlikely to be used because
of the difficulty of storing materials.
[0471] It is possible to use the organic peroxide (B) to conduct
peroxide crosslinking of a halogen-containing polymer such as a
fluorine rubber.
[0472] It is possible to use a polyol-based crosslinking agent to
conduct polyol crosslinking of a halogen-containing polymer such as
a fluorine rubber.
[0473] As a polyol-based crosslinking agent, bisphenols are
preferable. Specific examples thereof include, for example,
polyhydroxyaromatic compounds such as 2,2'-bis(4-hydroxyphenyl)
propan[bisphenol A], 2,2-bis(4-hydroxyphenyl)
hexafluoropropan[bisphenol AF], bis(4-hydroxyphenyl) sulfone
[bisphenol S], bisphenol A bis(diphenyl phosphate),
4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl methane, and
2,2-bis(4-hydroxyphenyl) butane[bisphenol B].
[0474] As a polyol-based crosslinking agent, preferably bisphenol A
or bisphenol AF is used. It is also possible to use, as a
polyol-based crosslinking agent, an alkali metal salt or an
alkaline-earth metal salt of the polyhydroxyaromatic compound.
[0475] It is also possible to use, as a polyol-based crosslinking
agent, a commercially available master batch containing a starting
material rubber and a polyol-based crosslinking agent. Examples of
a commercially available master batch include, for example,
Curative VC#30 (manufactured by DuPont Dow Elastomers L.L.C.:
containing 50 wt % of a crosslinking agent [bisphenol AF]).
[0476] Such crosslinking agents may be used singly or in
combination of the two or more kinds.
[0477] It is possible to use the following as a filler in the layer
(4): metallic hydroxides such as magnesium hydroxide, aluminum
hydroxide, and calcium hydroxide; carbonates such as magnesium
carbonate, aluminum carbonate, calcium carbonate, and barium
carbonate; silicates such as magnesium silicate, calcium silicate,
sodium silicate, aluminum silicate; sulfates such as aluminum
sulfate, calcium sulfate, and barium sulfate; metallic sulfides
such as synthetic hydrotalcite, molybdenum disulfide, iron sulfide,
and Copper sulfide; silicon oxides such as wet silica, dry silica,
fine quartz powder, and glass fibers; inorganic fillers such as
diatomous earth, asbestos, lithopone (zinc sulfide/barium sulfide),
graphite, carbon black, carbon fluoride, calcium fluoride, coke,
talc, mica powder, wollastonite, carbon fibers, aramid fibers, and
various whiskers, as well as, organic stiffeners and organic
fillers.
[0478] It is also possible to optionally add, as the other
component (J), an acid acceptor, an ultraviolet absorber, a flame
retardant, oil resistance improver, an antiscorching agent, a
tackifier, and the like to the halogen-containing polymer.
[0479] The layer (4) may be formed using a commercially available
composition containing a fluorine rubber which is a
halogen-containing polymer and a crosslinking agent. Examples of a
commercially available composition containing a fluorine rubber and
a crosslinking agent include, for example, DAI-EL DC-2270F and
DAI-EL DC-4070 (manufactured by Daikin Industries, Ltd.). DAI-EL
DC-2270F is a composition containing a polyol-based crosslinking
agent, a filler, and an acid acceptor, in addition to a fluorine
rubber. DAI-EL DC-4070 is a composition containing an organic
peroxide and a filler, in addition to a fluorine rubber.
(Method of Preparing Materials Constituting Each Layer)
[0480] A method of preparing materials constituting each layer is
not particularly limited. When the layer (1) consists of an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer, the layer
(2) consists of an ethylene/carboxylic acid copolymer, the layer
(3) consists of an acrylic-type rubber, and/or the layer (4)
consists of a halogen-containing polymer, the above-described
polymers (rubbers) can be directly used.
[0481] Materials constituting each layer can be prepared by the
following method when the materials include a component other than
any of the above-described polymers (rubbers), which means when the
layer (1) comprises a resin composition containing an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer, the layer
(2) comprises a resin composition containing an ethylene/carboxylic
acid copolymer, the layer (3) comprises a resin composition
containing an acrylic-type rubber, and/or the layer (4) comprises a
resin composition containing a halogen-containing polymer.
[0482] The resin composition can be prepared by appropriately
mixing: a polymer (rubber) (ethylene/.alpha.-olefin/non-conjugated
polyene copolymer (layer (1)), an ethylene/carboxylic acid
copolymer (layer (2)), an acrylic-type rubber (layer (3)), and a
halogen-containing polymer (layer (4))); (B) an organic peroxide,
(C) carbon black; (D) an antioxidant; (E) a softening agent; (F) a
metal oxide; (G) a crosslinking aid; (H) an onium salt; (I) an
inorganic compound containing oxygen and at least one element
selected from Group 2 elements and Group 13 elements; and (J) other
components.
[0483] Methods of preparing the resin composition include, but are
not particularly limited to, a method, such as a method of mixing
each component contained in the resin composition by using a
conventionally known kneading machine such as a mixer, a kneader,
and a roll, and a method of preparing a solution in which each
component contained in the resin composition is dissolved or
dispersed, followed by removing the solvent.
[0484] (Layered Product)
[0485] As described above, the layered product of this invention is
a layered product, which includes at least one type of layer
selected from the following layers (1) and (2), and further
includes at least one type of layer selected from the following
layers (3) and (4), wherein at least one layer of the at least one
type of layer selected from the layers (1) and (2) is directly in
contact with or adjacent via an adhesive layer to of the at least
one type of layer at least one layer selected from the layers (3)
and (4).
[0486] Layer (1): a layer prepared using an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer
[0487] Layer (2): a layer prepared using an ethylene/carboxylic
acid copolymer
[0488] Layer (3): a layer prepared using an acrylic-type rubber
[0489] Layer (4): a layer prepared using a halogen-containing
polymer
[0490] The layered product of this invention has at least one type
of layer selected from the layers (1) and (2) and at least one type
of layer selected from the layers (3) and (4). The layer
configuration of the layered product of this invention is not
particularly limited as long as the at least one layer of the at
least one type of layer selected from the layers (1) and (2) is
directly in contact with or adjacent via an adhesive layer to the
at least one layer of the at least one type of layer selected from
the layers (3) and (4).
[0491] The thickness of each layer constituting the layered product
is not particularly limited. However, the thickness of layer (1) is
usually 1 to 30 mm and preferably 3 to 10 mm, the thickness of
layer (2) is usually 1 to 30 mm and preferably 1 to 5 mm, the
thickness of layer (3) is usually 1 to 30 mm and preferably 1 to 5
mm, and the thickness of layer (4) is usually 1 to 30 mm and
preferably 1 to 5 mm. The total thickness of the layered product is
also not particularly limited. However, it is usually from 5 to 31
mm and preferably from 5 to 20 mm. In addition, in a case in which
the layered product has an adhesive layer, the thickness is, but is
not particularly limited to, usually from 0.1 to 10 .mu.m and
preferably from 0.1 to 5 mm.
[0492] In a preferred embodiment of the layered product of this
invention, the layer (1) and the layer (4) are directly in contact
with each other in the layered product. In a case in which a
fluorine rubber and a non-polar rubber are layered, it is common to
layer them via an adhesive layer. Nevertheless, the inventors found
that it is possible to directly bond the layer (1) and the layer
(4), which are used in combination, without providing an adhesive
layer.
[0493] A layered product, in which the layer (1) and the layer (4)
are directly in contact with each other, is not particularly
limited in terms of the layer configuration of the layered product
as a whole as long as it has a layer (1)/layer (4) configuration.
Examples of a layered product having a layer configuration in which
the layer (1) and the layer (4) are directly in contact with each
other include a layered product having a layer (1)/layer (4)
configuration, a layered product having a layer (1)/layer (4)/layer
(1) configuration, a layered product having a layer (4)/layer
(1)/layer (4) configuration, a layered product having a layer
(1)/layer (4)/layer (1)/layer (4) configuration, and a layered
product having a layer (1)/layer (4)/adhesive layer/layer (2)
configuration.
[0494] In another preferred embodiment of the layered product of
this invention, the layer (1) and the layer (3) are directly in
contact with each other in the layered product. The present
inventors found that it is possible to directly bond the layer (1)
and the layer (3), which are used in combination, without providing
an adhesive layer.
[0495] A layered product, in which the layer (1) and the layer (3)
are directly in contact with each other, is not particularly
limited in terms of the layer configuration of the layered product
as a whole as long as it has a layer (1)/layer (3) configuration.
Examples of a layered product having a layer configuration in which
the layer (1) and the layer (3) are directly in contact with each
other include a layered product having a layer (1)/layer (3)
configuration, a layered product having a layer (1)/layer (3)/layer
(1) configuration, a layered product having a layer (3)/layer
(1)/layer (3) configuration, a layered product having a layer
(1)/layer (3)/layer (1)/layer (3) configuration, and a layered
product having a layer (1)/layer (3)/adhesive layer/layer (2)
configuration.
[0496] In another preferred embodiment of the layered product of
this invention, at least one type of layer selected from the layers
(1) and (2) is bonded to the layer (3) via an adhesive layer in the
layered product. The present inventors found that the use of an
adhesive enables sufficient bonding in such embodiment.
[0497] A layered product, in which at least one type of layer
selected from the layer (1) and the layer (2) is bonded to the
layer (3) via an adhesive layer, is not particularly limited in
terms of the layer configuration of the layered product as a whole
as long as it has a layer (1) or (2)/adhesive layer/layer (3)
configuration. Examples of a layered product having a layer
configuration in which at least one type of layer selected from the
layer (1) and the layer (2) is bonded to the layer (3) via an
adhesive layer include a layered product having a layer (1) or
(2)/adhesive layer/layer (3) configuration, a layered product
having a layer (1) or (2)/adhesive layer/layer (3)/adhesive
layer/layer (1) or (2) configuration, a layered product having a
layer (3)/adhesive layer/layer (1) or (2)/adhesive layer/layer (3)
configuration, and a layered product having a layer (1) or
(2)/adhesive layer/layer (3)/adhesive layer/layer (1) or
(2)/adhesive layer/layer (3) configuration.
[0498] From a different viewpoint of a preferred embodiment of the
layered product of this invention, at least one type of layer
selected from the layers (1) and (2) contains 0.2 parts by mass or
more of an onium salt with respect to 100 parts by mass of the
copolymer, and an inorganic compound containing oxygen and at least
one element selected from Group 2 elements and Group 13 elements is
contained in an amount of 7 parts by mass or more with respect to
100 parts by mass of the copolymer in the layered product. The
layered product is more preferably a layered product, in which at
least one type of layer selected from the layers (1) and (2)
contains 0.2 to 10 parts by mass of an onium salt with respect to
100 parts by mass of the copolymer, and an inorganic compound
containing oxygen and at least one element selected from Group 2
elements and Group 13 elements is contained in an amount of 7 to
100 parts by mass with respect to 100 parts by mass of the
copolymer. When at least one type of layer selected from the layers
(1) and (2) contains an onium salt and an inorganic compound
containing oxygen and at least one element selected from Group 2
elements and Group 13 elements, adhesiveness to at least one type
of layer selected from the layers (3) and (4), and preferably the
layer (4), improves, which is preferable.
[0499] In a case in which a non-conjugated polyene of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer contained
in the layer (1) is VNB, which means that the copolymer is an
ethylene/.alpha.-olefin/VNB copolymer, the layered product has
excellent fatigue resistance, which is preferable. In a case in
which the B value of the ethylene/.alpha.-olefin/VNB copolymer is
particularly high, and specifically, the B value is from 1.22 to
1.40, the layered product has particularly excellent fatigue
resistance, which is preferable. The layered product is
particularly useful because it has more excellent fatigue
resistance than a conventionally known layered product in which an
acrylic rubber layer and a fluorine rubber layer are stacked.
[0500] In a case in which the layered product of this invention has
an adhesive layer, an adhesive constituting the adhesive layer is
not particularly limited. A commercially available product that can
be used as such adhesive is, for example, Chemlok XJ150
(manufactured by Chemlok)
[0501] (Method for Producing Layered Product)
[0502] A method for producing the layered product of this invention
is not particularly limited. However, examples of the method
include the following methods (a) to (e) comprising obtaining a
layered product. According to the methods (a) to (e), a
crosslinking step may be conducted after obtaining a layered
product. Alternatively, it is also possible to obtain a layered
product having a layer comprising a crosslinked polymer or rubber
by conducting a secondary vulcanization step in an oven or the like
after primary vulcanization. At least one type of layer selected
from the layer (1) and the layer (2) is also referred to as "layer
A," and at least one type of layer selected from the layer (3) and
the layer (4) is also referred to as "layer B."
[0503] (a) Method of obtaining a layered product, in which a layer
A and a layer B are directly in contact with each other, by
separately mixing materials constituting the layer A and materials
constituting the layer B by using a kneader, a roll, or a mixer
such as a Banbury mixer or an internal mixer and simultaneously
extruding the kneaded products by an extruder.
[0504] (b) Method of obtaining a layered product, in which a layer
A and a layer B are directly in contact with each other, by mixing
materials constituting the layer A by using a kneader, a roll, or a
mixer such as a Banbury mixer or an internal mixer and extruding
the kneaded product by an extruder to form the layer A, mixing
materials constituting the layer B by using a kneader, a roll, or a
mixer such as a Banbury mixer or an internal mixer, and extruding
the kneaded product on the layer A by an extruder.
[0505] (c) Method of obtaining a layered product, in which a layer
A and a layer B are directly in contact with each other, by mixing
materials constituting the layer B by using a kneader, a roll, or a
mixer such as a Banbury mixer or an internal mixer and extruding
the kneaded product by an extruder to form the layer B, mixing
materials constituting the layer A by using a kneader, a roll, or a
mixer such as a Banbury mixer or an internal mixer, and extruding
the kneaded product on the layer B by an extruder.
[0506] (d) Method of obtaining a layered product, in which a layer
A and a layer B are adjacent to each other via an adhesive layer,
by mixing materials constituting the layer A by using a kneader, a
roll, or a mixer such as a Banbury mixer or an internal mixer and
extruding the kneaded product by an extruder to form the layer A,
mixing materials constituting the layer B by using a kneader, a
roll, or a mixer such as a Banbury mixer or an internal mixer and
extruding the kneaded product by an extruder to form the layer B,
and directly bonding the layer A and the layer B.
[0507] (e) Method of obtaining a layered product, in which a layer
A and a layer B are adjacent to each other via an adhesive layer,
by mixing materials constituting the layer A by using a kneader, a
roll, or a mixer such as a Banbury mixer or an internal mixer and
extruding the kneaded product by an extruder to form the layer A,
mixing materials constituting the layer B by using a kneader, a
roll, or a mixer such as a Banbury mixer or an internal mixer and
extruding the kneaded product to form the layer B, and bonding the
layer A and the layer B using an adhesive.
[0508] When a layered product is produced, it is preferable to
conduct press shaping of a layered produce in which the layer A and
the layer B are adjacent to each other directly or via an adhesive
layer in view of the improvement of peel strength between the layer
A the layer B.
[0509] (Crosslinked Step or Primary Vulcanization)
[0510] A crosslinked step or primary vulcanization is a step of
preliminarily adding components necessary for crosslinking such as
a crosslinking agent to materials constituting the layer A and
materials constituting the layer B and performing crosslinking by
heating (for example, 150.degree. C. to 240.degree. C.), a step of
irradiating a layered product with an electron beam (for example,
an electron beam having an energy of 0.1 to 10 MeV) to perform
crosslinking, or the like. Irradiation with the electron beam is
carried out so that the dose absorbed into the resin composition
may be usually 0.5 to 36 Mrads, preferably 0.5 to 20 Mrads, and
more preferably 1 to 10 Mrads.
[0511] When crosslinking is carried out by heating during the
crosslinked step or primary vulcanization, it is preferable to
carry out heating while conducting press-shaping in view of the
improvement of peel strength between the layer A and the layer
B.
[0512] (Secondary Vulcanization)
[0513] Secondary vulcanization is a step carried out after the
primary vulcanization for sufficiently improving vulcanization
(crosslinking) by performing heating (for example, 150.degree. C.
to 200.degree. C.)
<Application>
[0514] As the layered product of this invention can satisfy various
required characteristics because of its layer configuration, it can
be used for various applications.
[0515] The layered product of this invention can be used for
various applications. The layered product of this invention can be
used for members of automobiles, motorbikes, industrial machinery,
construction machinery, agricultural machinery, and the like.
Specific examples of the members include rolls for industrial use,
packings (for example, capacitor packing), gaskets, belts (for
example, heat-insulating belt, belt for copying machines, and
conveyance belt), hoses such as hoses for cars (for examples,
turbocharger hose, water hose, brake reservoir hose, radiator hose,
and air hose), anti-vibration rubbers, anti-vibration or
vibration-controlling materials (for example, engine mount and
motor mount), muffler hangers, cables (ignition cable, cabtire
cable, and high tension cable), materials for wire cover (materials
for covering high voltage wire, low voltage wire, and wire used in
vessels), glass run channels, colored skin materials, paper-feeding
rolls, and roofing sheets.
[0516] The ethylene/.alpha.-olefin/non-conjugated polyene copolymer
also enables obtaining a crosslinked article excellent not only in
moldability and crosslinking property, but also in thermal
stability, and therefore, the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer having a
layer (1) can be suitably used in applications in which their
long-term use under high temperature is expected. In a case in
which the ethylene/.alpha.-olefin/non-conjugated polyene copolymer
is an ethylene/.alpha.-olefin/VNB copolymer, it is particularly
excellent in terms of fatigue resistance, which means that the
layered product can be usable under extreme condition for a long
period of time. This is preferable.
[0517] The layered product of this invention is suitably used for
automotive interior and exterior parts and applications requiring
heat resistance among others. An example application of the layered
product is a hose which includes the layered product of this
invention at least as a part thereof. Although the hose does not
have any particular limitation in its use, it is preferably a hose
used in any one of applications for automobiles, motorbikes,
industrial machinery, construction machinery, and agricultural
machinery. More specifically, it is suitably used in applications
for hoses including the turbocharger hose, the brake reservoir
hose, and the radiator hose, and particularly suitably used in the
turbocharger hose for automobiles.
[0518] The hose of this invention may include the layered product
of this invention as at least a part thereof, and it may be a hose
consisting of the layered product of this invention.
[0519] The turbocharger hose of this invention has a multilayer
structure including preferably a layer composed of a crosslinked
article of a composition comprising an
ethylene/.alpha.-olefin/non-conjugated polyene copolymer and a
layer composed of a different material such that it can endure
extreme use conditions under high temperature and high pressure. In
the layered product of this invention, only one layer may be formed
with a crosslinked article, or two or more layers may be formed
with a crosslinked article.
[0520] Methods of producing the turbocharger hose of this invention
does not have any particular limitation, and they include, for
example, a method of obtaining a turbocharger hose (layered
product), which method shapes an uncured layer-structured
turbocharger hose by using extrusion molding, coextrusion molding,
winding of a sheet material, or a combination thereof, and then
heats it by using steam among others. The uncured turbocharger hose
is preferably highly capable of retaining its shape without
shrinking or deformation.
EXAMPLES
[0521] Although this invention will be described more specifically
based on the following Examples, the invention is not limited
thereto.
(Measurement and Evaluation Method)
[0522] In Production Examples, Examples, and Comparative Examples
below, measurement and evaluation methods of respective
characteristics are as follows.
[0523] (Composition of Ethylene/.alpha.-Olefin/Non-Conjugated
Polyene Copolymer and B Value)
[0524] The mass fraction (% by mass) of each structural unit of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer and the B
value were determined from measurement values by using
.sup.13C-NMR. The measurement values were obtained by measuring the
.sup.13C-NMR spectrum of the copolymer by using a nuclear magnetic
resonance apparatus, Model ECX400P (manufactured by JEOL Ltd.) at a
measurement temperature of 120.degree. C., in a measurement solvent
of orthodicholorbenzene/deuterated benzene=4/1, with a cumulative
number of 8,000.
[0525] (Intrinsic Viscosity [.eta.])
[0526] The intrinsic viscosity [.eta.] (dl/g) of the
ethylene/.alpha.-olefin/non-conjugated polyene copolymer was
measured by using a fully automated intrinsic viscometer
manufactured by RIGO CO., LTD., at a temperature of 135.degree. C.
in a measurement solvent of decalin.
[0527] (Weight-Average Molecular Weight (Mw), Number-Average
Molecular Weight (Mn), and Molecular Weight Distribution
(Mw/Mn))
[0528] The weight-average molecular weight (Mw), the number-average
molecular weight (Mn), and the molecular weight distribution
(Mw/Mn) are numerical values in terms of polystyrene, measured by
gel permeation chromatography (GPC). The measuring apparatus and a
measurement condition are as follows. The molecular weight was
calculated based on the conversion method using a calibration curve
generated by using commercial monodispersed polystyrene.
[0529] Apparatus: gel permeation chromatograph Model Alliance
GP2000 (manufactured by Waters),
[0530] Analyzer: Empower2 (manufactured by Waters),
[0531] Column: TSKgel GMH6-HT x 2+TSKgel GMH6-HTL x 2 (7.5 mm I.D.
30 cm, manufactured by Tosoh Corporation),
[0532] Column temperature: 140.degree. C.,
[0533] Mobile phase: o-dichlorobenzene (containing 0.025% of
BHT),
[0534] Detector: refractive index detector (RI), Flow rate: 1.0
mL/min,
[0535] Load quantity: 400 .mu.L,
[0536] Sampling interval: 1 s,
[0537] Column calibration: monodispersed polystyrene (manufactured
by Tosoh Corporation),
[0538] Molecular-weight: expressed in terms of EPR in the old
method/calibrating method taking viscosity into account.
[0539] (T-Peel Test)
[0540] Peel strength of the layered products was measured by the
method described below.
[0541] T-peel test of the layered products obtained in the Examples
and Comparative Examples was conducted for determining peel
strength: measurement temperature: 23.0.degree. C.; test speed:
200.0 ram/min; and test piece width: 80.0 mm.
[0542] (Surface Swelling Test)
[0543] Surface swelling test of the layered products was conducted
by the method described below.
[0544] The crosslinked rubber sheets (layered product) 5 mm in
thickness obtained in the Examples and Comparative Examples were
cut into 8 cm.times.8 cm square pieces, thereby obtaining layered
products for measurement.
[0545] A circular embankment was made using a silicone sealant on a
layer B of each layered product for measurement. The embankment was
formed on the layer B such that it had an inner diameter of 5 cm
and a height of about 2 cm.
[0546] A lubricant (IRM903 manufactured by Japan Sun Oil Company,
Ltd.) in an amount of 2.4 g was poured inside the embankment.
[0547] Temperature was maintained at 80.degree. C. and the surface
condition was observed 1 hour later.
[0548] Visual observation was conducted by evaluating a case in
which the layered product surface appeared in the form of a
protrusion due to swelling of the rubber of the layered product
above the lubricant surface as "x" (swelling) and a case in which
the layered product did not appear above the lubricant surface as
"o" (no swelling).
[0549] (Modulus, Tensile Strength at Break, Tensile Elongation at
Break)
[0550] Modulus, tensile strength at break, and tensile elongation
at break of the sheets were measured by the methods described
below.
[0551] Each sheet was punched out to prepare a dumbbell test piece
of Type 3 described in JIS K 6251 (1993), which was used for a
tensile test, to measure tensile stress (100% modulus (M100)) at a
tension rate of 100%, tensile stress (200% modulus (M200)) at a
tension rate of 200%, tensile stress (300% modulus (M300)) at a
tension rate of 300%, tensile strength at break (TB), and tensile
elongation at break (EB) under a condition of a measurement
temperature of 25.degree. C. and a tensile speed of 500 mm/minute
according to the method specified in the section 3 of JIS K
6251.
[0552] (Hardness Test (Shore A Hardness))
[0553] According to JIS K 6253, sheet hardness (Type A durometer,
HA) was measured by using a test piece of about 12 mm in thickness,
which was made of six sheet-like rubber shaped articles of 2 mm in
thickness having a smooth surface, the rubber shaped articles being
stacked on the top of a flat portion of each other. A test piece
which was contaminated by foreign substances, or which had foams or
a scratch was not used. The dimension of the measurement surface of
the test piece was taken to be large enough so that a pressure
needle tip might enable measuring the hardness at a point distant
by 12 mm or more from the edge of the test piece.
[0554] (Heat Aging Resistance Test)
[0555] A heat aging resistance test was carried out according to
JIS K 6257. Specifically, each sheet was placed in an oven at
180.degree. C. for 168 hours to be aged, and then a tensile test
was carried out under a condition of a measurement temperature of
23.degree. C., a tension rate of 500 mm/minute, to measure tensile
strength at break (TB) and tensile elongation at break (EB).
Further, hardness was measured by the same method as in the
above-described section (Hardness test (Shore A hardness)).
[0556] (Flexural Fatigue Resistance)
[0557] In accordance with JIS K 6260, the resistance against crack
generation of a test piece having no groove and the crack growth
thereof were evaluated which were observed when repeated bending
was given to the test piece by using a Demacha type bending tester.
The measurement temperature was 23.degree. C. and the number of
cases in which the test piece was cut off was recorded.
[0558] Note that in a case in which the test piece was not cut off
even after bending for 500,000 times, the test was terminated and
the condition of the test piece was visually confirmed.
Production Example 1
[0559] (Production of Ethylene/Propylene/VNB Copolymer (A-1))
[0560] A continuous polymerization reaction of ethylene, propylene,
and 5-vinyl-2-norbornene (VNB) was carried out at 87.degree. C. by
using a 300 L polymerization vessel equipped with a stirring
blade.
[0561] The polymerization vessel was continuously fed with ethylene
so that its feed rate might be 3.6 kg/h, propylene 6.1 kg/h, VNB
290 g/h, and hydrogen 6.3 NL/h, with hexane as a polymerization
solvent (feed rate: 32.6 L/h).
[0562] The polymerization vessel was continuously fed with
di(p-tolyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride as a main
catalyst so that its feed rate might be 0.0015 mmol/h, with a
polymerization pressure kept to be 1.6 MPaG and a polymerization
temperature 87.degree. C. Further, the polymerization vessel was
continuously fed with
(C.sub.6H.sub.5).sub.3CB(C.sub.6F.sub.5).sub.4 as a co-catalyst so
that its feed rate might be 0.0075 mmol/h, and triisobutyl aluminum
(TIBA) as an organoaluminum compound 20 mmol/h.
[0563] In this way, a solution was obtained which contained 15.2%
by mass of ethylene/propylene/VNB copolymer formed from ethylene,
propylene, and VNB. A small amount of methanol was added to the
polymerization reaction solution extracted from the bottom of the
polymerization vessel, to quench the polymerization reaction, and
the ethylene/propylene/VNB copolymer was separated from the solvent
by a steam stripping treatment, and then dried under reduced
pressure at 80.degree. C. for 24 hours.
[0564] By the above operation, ethylene/propylene/VNB copolymer
(A-1) formed from ethylene, propylene, and VNB was obtained at a
rate of 4.7 kg/hr.
[0565] Physical properties of the obtained copolymer (A-1) were
measured by the aforementioned methods. The results are listed in
Table 1.
[0566] Hereinafter, the obtained copolymer (A-1) was also referred
to as "VNB-EPT."
TABLE-US-00001 TABLE 1 Copolymer A-1 Ethylene content [% by 73.8
mass] Ethylene/Propylene [molar 68/32 ratio] VNB content [% by
mass] 1.43 [.eta.] [dl/g] 2.88 Mw 318000 Mw/Mn 2.62 B value
1.20
[0567] In the Examples and Comparative Examples, the following
commercially available products were used as well as the copolymer
(A-1).
[0568] (Ethylene/.alpha.-Olefin/Non-Conjugated Polyene
Copolymer)
[0569] Mitsui EPT 2060M: ethylene/propylene/ENB copolymer with
ML(1+4) 125.degree. C. (ASTM D 1646) of 40, an ethylene content
(ASTM D 3900) of 55 wt %, an ENB content (ASTM D 6047) of 2.3 wt %
manufactured by Mitsui Chemicals, Inc.
[0570] Physical properties of Mitsui EPT 2060M are listed in Table
2.
[0571] Hereinafter, Mitsui EPT 2060M is also referred to as
"ENB-EPT."
TABLE-US-00002 TABLE 2 Copolymer 2060M Ethylene content [% by 55
mass] Ethylene/Propylene [molar 66/34 ratio] ENB content [% by
mass] 2.3 [.eta.] [dl/g] 2.16 Mw 161000 Mw/Mn 2.70 B value 1.00
[0572] (Acrylic-Type Rubber)
[0573] Vamac G: Composition containing ethylene acrylic rubber
manufactured by DuPont
[0574] Nipol AR-12: Acrylic rubber containing alkyl acrylate as a
main skeletal component manufactured by Zeon Corporation
[0575] Hereinafter, Vamac G is also referred to as "AEM" and Nipol
AR-12 is also referred to as "ACM."
[0576] (Fluorine Rubber)
[0577] Viton GBL-200S: Copolymer of hexafluoropropylene, vinylidene
fluoride, tetrafluoroethylene, and a monomer to be a cured portion
(olefin bromide) manufactured by DuPont
[0578] Hereinafter, Viton GBL-200S is also referred to as
"FKM."
Example 1
[0579] (Preparation of Composition Containing VNB-EPT)
[0580] As a first step, 100 parts by mass of VNB-EPT was roughly
kneaded for 30 seconds by a Banbury mixer, Model BB-2 (manufactured
by KOBE STEEL, LTD.), to which copolymer were added 60 parts by
mass of HAF carbon black (Asahi #70G, manufactured by Asahi Carbon
Co., Ltd.), 5 parts by mass of zinc flower (manufactured by
Hakusuitech Co., Ltd.), 1 part by mass of stearic acid, and 4 parts
by mass of 4,4'-bis(.alpha.,.alpha.-dimethylbenzyl)diphenylamine
(NOCRAC CD manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO.,
LTD.), and then kneaded at 140.degree. C. for 2 minutes. Then, the
ram of the mixer was raised to be cleaned, and they were kneaded
for one more minute, and discharged at about 150.degree. C. to
yield a compound of the first step.
[0581] Next, as a second step, the compound obtained in the first
step was banded on a roll of an 8-inch roll mill (manufactured by
Nippon Roll MFG. Co., Ltd., operating with a front roll at a
surface temperature of 50.degree. C. and a rotational rate of 16
rpm and a back roll at a surface temperature of 50.degree. C. and a
rotational rate of 18 rpm), and master batch (DCP-40c manufactured
by Kayaku Akzo Corporation) containing 40% by mass of dicumyl
peroxide as 3.4 parts by mass of the organic peroxide component
(1.36 parts by mass in terms of organic peroxide) was added to the
compound, which was then kneaded for 10 minutes to yield an
uncrosslinked resin composition (rubber compound) (composition
containing VNB-EPT).
[0582] (Preparation of Composition Containing AEM)
[0583] As a first step, 100 parts by mass of AEM was roughly
kneaded for 30 seconds by a Banbury mixer, Model BB-2 (manufactured
by KOBE STEEL, LTD.), to which copolymer were added 60 parts by
mass of HAF carbon black (Asahi #70G, manufactured by Asahi Carbon
Co., Ltd.), 1 part by mass of stearic acid, and 2 parts by mass of
4,4'-bis (.alpha.,.alpha.-dimethylbenzyl) diphenylamine (NOCRAC CD
manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.), and
then kneaded at 140.degree. C. for 2 minutes. Then, the ram of the
mixer was raised to be cleaned, and they were kneaded for one more
minute, and discharged at about 150.degree. C. to yield a compound
of the first step.
[0584] Next, as a second step, the compound obtained in the first
step was banded on a roll of an 8-inch roll mill (manufactured by
Nippon Roll MFG. Co., Ltd., operating with a front roll at a
surface temperature of 50.degree. C. at a rotational rate of 16 rpm
and a back roll at a surface temperature 50.degree. C. and a
rotational rate of 18 rpm), and 0.5 parts of Diak No. 1 (DuPont)
and 2.0 parts of NOCCELER-DT (Ouchi Shinko Chemical Industrial Co.,
Ltd.) were added to the compound, which was then kneaded for 10
minutes to yield an uncrosslinked resin composition (rubber
compound) (composition containing AEM).
[0585] (Preparation and Evaluation of Layered Product)
[0586] (Preparation of Layered Product for T-Peel Test)
[0587] The composition containing VNB-EPT and the composition
containing AEM were each sheeted into a sheet-like shape. Next, 50
g of each of the unvulcanized rubber sheets (the sheets of the
composition containing VNB-EPT and the composition containing AEM)
was sandwiched between LUMIRRORs (stretched polyester (polyethylene
terephthalate) film). Each unvulcanized rubber sheet sandwiched
between LUMIRRORs was pressed at 120.degree. C. for 2 minutes using
a 50-ton press-shaping machine to prepare a unvulcanized rubber
sheet in 20 cm in square (t (thickness)=1 mm).
[0588] Next, the unvulcanized rubber sheet obtained from the
composition containing VNB-EPT (layer A) and the pressed
unvulcanized rubber sheet obtained from the composition containing
AEM (B layer) after the press were each cut into the press size
described below (15 cm.times.15 cm x t=mm). After cutting, the
upper-side and lower-side LUMIRRORs were removed, and then the
respective unvulcanized rubber sheets were stacked on each other.
The unvulcanized rubber sheets were stacked on each other in a
manner such that a Teflon (registered trademark) resin sheet (t=0.2
mm) is sandwiched between the unvulcanized rubber sheets at a
certain part (width of 3 cm, length of 15 cm: margin for peel
test).
[0589] The stacked unvulcanized rubber sheets sandwiching the
Teflon (registered trademark) resin sheet at the certain part was
pressed (main press) at 180.degree. C. for 10 minutes using a
100-ton press-shaping machine to prepare a crosslinked rubber sheet
(layered product) of 2 mm in thickness.
[0590] The Teflon (registered trademark) resin sheet was removed
from the resulting crosslinked rubber sheet (layered product), and
T-peel test of the crosslinked rubber sheet (layered product) was
conducted.
[0591] (Preparation of Layered Product for Surface Swelling
Test)
[0592] The composition containing VNB-EPT was sheeted into a
sheet-like shape. Next, 200 g of the unvulcanized rubber sheet (the
sheets of the composition containing VNB-EPT) was sandwiched
between LUMIRRORs (stretched polyester (polyethylene terephthalate)
film). The unvulcanized rubber sheet sandwiched between LUMIRRORs
was pressed at 120.degree. C. for 2 minutes using a 50-ton
press-shaping machine to prepare a unvulcanized rubber sheet (layer
A) in 20 cm in square (t (thickness)=4 mm).
[0593] The composition containing AEM was sheeted into a sheet-like
shape. Next, 50 g of the unvulcanized rubber sheet (the sheets of
the composition containing AEM) was sandwiched between LUMIRRORs
(stretched polyester (polyethylene terephthalate) film). The
unvulcanized rubber sheet sandwiched between LUMIRRORs was pressed
at 120.degree. C. for 2 minutes using a 50-ton press-shaping
machine to prepare a unvulcanized rubber sheet (layer B) in 20 cm
in square (t (thickness)=1 mm).
[0594] After LUMIRRORs on the upper side and lower side of each of
the unvulcanized rubber sheets (layer A and layer B) were removed,
the unvulcanized rubber sheet (layer A) obtained from the
composition containing VNB-EPT and the unvulcanized rubber sheet
(layer B) obtained from the composition containing AEM were stacked
and pressed at 180.degree. C. for 10 minutes using a 100-ton
press-shaping machine to prepare a crosslinked rubber sheet
(layered product) of 5 mm in thickness. A surface swelling test of
a crosslinked shaped article was conducted using the obtained
product.
Example 2
[0595] A composition containing VNB-EPT and a composition
containing AEM were prepared in the same manner as in Example
1.
[0596] (Preparation and Evaluation of Layered Product)
[0597] (Preparation of Layered Product for T-Peel Test)
[0598] The unvulcanized rubber sheet (layer A) obtained from the
composition containing VNB-EPT and the unvulcanized rubber sheet
(layer B) obtained from the composition containing AEM, which were
cut into a main press size (15 cm.times.15 cm x t=1 mm), were
obtained by the same method as in Example 1.
[0599] An adhesive (Chemlok XJ150 (manufactured by Chemlok)) was
applied to one side of the layer A using a brush and dried for 10
minutes. Then, the cut unvulcanized rubber sheets were stacked
thereon. The unvulcanized rubber sheets were stacked on each other
in a manner such that a Teflon (registered trademark) resin sheet
(t=0.2 mm) is sandwiched between the unvulcanized rubber sheets at
a certain part (width of 3 cm, length of 15 cm: margin for peel
test). In addition, the layer A and the layer B were stacked such
that they were adjacent via the adhesive.
[0600] The crosslinked rubber sheet (layered product) of 2 mm in
thickness was obtained from the stacked unvulcanized rubber sheets
sandwiching the Teflon (registered trademark) resin sheet at the
certain part by the same method as in Example 1.
[0601] The Teflon (registered trademark) resin sheet was removed
from the resulting crosslinked rubber sheet (layered product), and
T-peel test of the crosslinked rubber sheet (layered product) was
conducted.
[0602] (Preparation of Layered Product for Surface Swelling
Test)
[0603] The unvulcanized rubber sheet (layer A) obtained from the
composition containing VNB-EPT and the unvulcanized rubber sheet
(layer B) obtained from the composition containing AEM were
obtained by the same method as in Example 1.
[0604] An adhesive (Chemlok XJ150 (manufactured by Chemlok)) was
applied to one side of the layer A using a brush and dried for 10
minutes. Then, the unvulcanized rubber sheet (layer A) obtained
from the composition containing VNB-EPT and the unvulcanized rubber
sheet (layer B) obtained from the composition containing AEM were
stacked such that the layer A and the layer B were adjacent to each
other via an adhesive, and pressed at 180.degree. C. for 10 minutes
using a 100-ton press-shaping machine to prepare a crosslinked
rubber sheet (layered product) of 5 mm in thickness. A surface
swelling test of a crosslinked shaped article was conducted using
the obtained product.
Example 3
[0605] A composition and a sheet (layered product) were prepared
and physical properties thereof were evaluated in the same manner
as in Example 1 except that AEM in Example 1 was replaced by
ACM.
Example 4
[0606] A composition and a sheet (layered product) were prepared
and physical properties thereof were evaluated in the same manner
as in Example 2 except that AEM in Example 2 was replaced by
ACM.
Example 5
[0607] A composition and a sheet (layered product) were prepared
and physical properties thereof were evaluated in the same manner
as in Example 1 except that AEM in Example 1 was replaced by FKM.
Note that in consideration of specific gravities of AEM and FKM, 50
g of the unvulcanized rubber sheet (a sheet of a composition
containing AEM) sheeted in Example 1 was replaced by 100 g of the
sheeted unvulcanized rubber sheet (a sheet of a composition
containing FKM).
Example 6
[0608] A composition and a sheet (layered product) were prepared
and physical properties thereof were evaluated in the same manner
as in Example 5 except that VNB-EPT in Example 5 was replaced by
ENB-EPT.
Reference Example 1
[0609] A composition and a sheet (layered product) were prepared
and physical properties thereof were evaluated in the same manner
as in Example 1 except that VNB-EPT in Example 1 was replaced by
AEM, and AEM in Example 1 was replaced by FKM. Note that in
consideration of specific gravities of AEM and FKM, 50 g of the
unvulcanized rubber sheet (a sheet of a composition containing AEM)
sheeted in Example 1 was replaced by 100 g of the sheeted
unvulcanized rubber sheet (a sheet of a composition containing
FKM).
Comparative Example 1
[0610] A composition containing VNB-EPT was prepared in the same
manner as in Example 1.
[0611] A composition containing VNB-EPT was sheeted into a
sheet-like shape and pressed at 120.degree. C. for 2 minutes using
a 50-ton press-shaping machine to prepare an unvulcanized rubber
sheet in 20 cm in square sandwiched with LUMIRROR (t=5 mm) (A
layer).
[0612] Next, the unvulcanized rubber sheet (layer A) obtained from
the composition containing VNB-EPT was pressed at 180.degree. C.
for 10 minutes using a 100-ton press-shaping machine to prepare a
crosslinked rubber sheet (monolayer product) of 5 mm in thickness.
A surface swelling test of a crosslinked shaped article was
conducted using the obtained product.
TABLE-US-00003 TABLE 3 Reference Comparative Example 1 Example 2
Example 3 Example 4 Example 5 Example 6 Example 1 Example 1 Layer A
VNB-EPT VNB-EPT VNB-EPT VNB-EPT VNB-EPT ENB-EPT AEM VNB-EPT Layer B
AEM AEM ACM ACM FKM FKM FKM Not used Adhesive Not used Used Not
used Used Not used Not used Not used -- T-peel test N/cm 3.7 34.4
0.5 0.5 20.4 19.5 29.0 -- Surface swelling test (.smallcircle.: No
swelling, x: Swelling) Test oil IRM903: 2.4 g 80.degree. C., 3 h
later .smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. x 80.degree. C., 6 h
later .smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. x 80.degree. C., 9 h
later .smallcircle. .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. x
Example 7
[0613] (Preparation of Composition Containing VNB-EPT)
[0614] As a first step, 100 parts by mass of VNB-EPT was roughly
kneaded for 1 seconds by a Banbury mixer, Model BB-2 (manufactured
by KOBE STEEL, LTD.), to which copolymer were added 30 parts by
mass of FEF carbon black (Asahi #60G, manufactured by Asahi Carbon
Co., Ltd.), 45 parts by mass of SRF carbon black (Asahi #50G,
manufactured by Asahi Carbon Co., Ltd.), 40 parts by mass of FT
carbon black (Asahi #15HS, manufactured by Asahi Carbon Co., Ltd.),
5 parts by mass of zinc flower (manufactured by Hakusuitech Co.,
Ltd.), 1 part by mass of stearic acid, and 4 parts by mass of
4,4'-bis (.alpha.,.alpha.-dimethylbenzyl) diphenylamine (NOCRAC CD
manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.), 3
parts by mass of LIPOQUAD 2HTF (manufactured by Lion Specialty
Chemicals Co., Ltd.), and 47 parts by mass of Diana Process Oil
PS-430 (manufactured by Idemitsu Kosan Co., Ltd.), and they were
kneaded at 140.degree. C. for 2 minutes. Then, the ram of the mixer
was raised to be cleaned, and they were kneaded for one more
minute, and discharged at about 150.degree. C. to yield a compound
of the first step.
[0615] Next, as a second step, the compound obtained in the first
step was banded on an roll of an 8-inch roll mill (manufactured by
Nippon Roll MFG. Co., Ltd., operating with a front roll at a
surface temperature of 50.degree. C. and a rotational rate of 18
rpm and aback roll at a surface temperature of 50.degree. C. and a
rotational rate of 15 rpm), and master batch (perhexa 25B-40,
Manufactured by NOF Corporation) (2.2 parts by mass in terms of
organic peroxide) containing 40% by mass of
2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane as 5.5 parts by mass
of the organic peroxide component (2.2 parts by mass in terms of
organic peroxide) was added to the compound, which was then kneaded
for 10 minutes to yield an uncrosslinked resin composition (rubber
compound) (composition containing VNB-EPT).
[0616] (Composition Containing Fluorine Rubber)
[0617] As a composition containing fluorine rubber, DAI-EL DC-2270F
(manufactured by Daikin Industries, Ltd.: polyol crosslinked-type
fluorine rubber compound) was used. DAI-EL DC-2270F is a
composition containing a polyol-based crosslinking agent (bisphenol
AF), a crosslinking enhancer (quaternary onium salt), a filler, and
an acid acceptor, in addition to fluorine rubber.
[0618] (Preparation and Evaluation of Layered Product)
[0619] (Preparation of Layered Product for T-Peel Test)
[0620] The composition containing VNB-EPT and the composition
containing fluorine rubber were each sheeted into a sheet-like
shape. Next, 100 g of each of the unvulcanized rubber sheets (the
sheets of the composition containing VNB-EPT and the composition
containing fluorine rubber) was sandwiched between LUMIRRORs
(stretched polyester (polyethylene terephthalate) film). Each
unvulcanized rubber sheet sandwiched between LUMIRRORs was pressed
at 120.degree. C. for 2 minutes using a 50-ton press-shaping
machine to prepare a unvulcanized rubber sheet in 20 cm in square
(t (thickness)=1 mm).
[0621] Next, the unvulcanized rubber sheet obtained from the
composition containing VNB-EPT (layer A) and the pressed
unvulcanized rubber sheet obtained from the composition containing
fluorine rubber (layer B) after the press were each cut into the
press size described below (15 cm.times.15 cm x t=1 mm). After
cutting, the upper-side and lower-side LUMIRRORs were removed, and
then the respective unvulcanized rubber sheets were stacked on each
other. The unvulcanized rubber sheets were stacked on each other in
a manner such that a Teflon (registered trademark) resin sheet
(t=0.2 mm) is sandwiched between the unvulcanized rubber sheets at
a certain part (width of 3 cm, length of 15 cm: margin for peel
test).
[0622] The stacked unvulcanized rubber sheets sandwiching the
Teflon (registered trademark) resin sheet at the certain part was
pressed (main press) at 180.degree. C. for 10 minutes using a
100-ton press-shaping machine to prepare a primarily vulcanized
crosslinked rubber sheet (layered product) of 2 mm in
thickness.
[0623] The Teflon (registered trademark) resin sheet was removed
from the resulting crosslinked rubber sheet (layered product), and
the crosslinked rubber sheet (layered product) was placed in an
oven at 180.degree. C. for 4 hours for carrying out secondary
vulcanization to yield a crosslinked rubber sheet (layered
product).
[0624] Two primarily vulcanized crosslinked rubber sheets (layered
products) and two secondarily vulcanized crosslinked rubber sheets
(layered products) were produced, and T-peel test of these
crosslinked rubber sheets (layered products) was conducted.
Example 8
[0625] (Preparation of Composition Containing VNB-EPT)
[0626] An uncrosslinked resin composition (rubber compound)
(composition containing VNB-EPT) was obtained in the same manner as
in Example 7 except that LIPOQUAD 2HTF was not used.
[0627] (Composition Containing Fluorine Rubber)
[0628] As a composition containing fluorine rubber, DAI-EL DC-4070
(manufactured by Daikin Industries, Ltd.) was used. DAI-EL DC-4070
is a composition containing an organic peroxide
(2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane) and a filler, in
addition to fluorine rubber.
[0629] (Preparation and Evaluation of Layered Product)
[0630] (Preparation of Layered Product for T-Peel Test)
[0631] A crosslinked rubber sheet (layered product) was obtained
using the composition containing VNB-EPT and the composition
containing fluorine rubber in the same method as in Example 7, and
T-peel test of a primarily vulcanized crosslinked rubber sheet
(layered product) and a secondarily vulcanized crosslinked rubber
sheet (layered product) thereof was conducted.
TABLE-US-00004 TABLE 4 Example 7 Example 8 [Composition formulation
containing VNB-EPT] VNB-EPT Parts by 100 100 mass Stearic acid
Parts by 1 1 mass MgO Parts by 5 5 mass FEF carbon (Asahi Parts by
30 30 60G) mass SRF carbon (Asahi Parts by 45 45 50G) mass FT
carbon (Asahi Parts by 40 40 15HS) mass NOCRAC CD Parts by 4 4 mass
LIPOQUAD 2HTF Parts by 3 mass PS-430 Parts by 47 47 mass PERHEXA
25B40 Parts by 5.5 5.5 mass Total 280.5 277.5 Composition DC2270F
DC4070 containing fluorine rubber Primarily Primarily vulcanized
vulcanized product product T-peel test N/cm 6.1 23.7 N/cm 6.3 20.6
Average 6.2 22.2 Secondarily Secondarily vulcanized vulcanized
product product N/cm 12.3 26.4 N/cm 11.7 26.6 Average 12.0 26.5
Example 9
[0632] As a first step, 100 parts by mass of VNB-EPT was roughly
kneaded for 30 seconds by a Banbury mixer, Model BB-2 (manufactured
by KOBE STEEL, LTD.), to which copolymer were added 60 parts by
mass of HAF carbon black (Asahi #70G, manufactured by Asahi Carbon
Co., Ltd.), 5 parts by mass of zinc flower, 1 part by mass of
stearic acid, and 4 parts by mass of 4,4'-bis
(.alpha.,.alpha.-dimethylbenzyl) diphenylamine (NOCRAC CD
manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.), and
then kneaded at 140.degree. C. for 2 minutes. Then, the ram of the
mixer was raised to be cleaned, and they were kneaded for one more
minute, and discharged at about 150.degree. C. to yield a compound
of the first step.
[0633] Next, as a second step, the compound obtained in the first
step was banded on a roll of an 8-inch roll mill (manufactured by
Nippon Roll MFG. Co., Ltd., operating with a front roll at a
surface temperature of 50.degree. C. and a rotational rate of 16
rpm and a back roll at a surface temperature of 50.degree. C. and a
rotational rate of 18 rpm), and master batch (DCP-40c manufactured
by Kayaku Akzo Corporation) containing 40% by mass of dicumyl
peroxide as 3.4 parts by mass of the organic peroxide component
(1.36 parts by mass in terms of organic peroxide) was added to the
compound, which was then kneaded for 10 minutes to yield an
uncrosslinked resin composition (rubber compound).
[0634] This resin composition was sheeted into a sheet-like shape
and pressed at 180.degree. C. for 10 minutes using a 100-ton
press-shaping machine to prepare a crosslinked rubber sheet of 2 mm
in thickness. This sheet was used to evaluate various physical
properties of the crosslinked shaped article. The results are
listed in Table 5.
Example 10
[0635] A crosslinked rubber sheet was obtained in the same manner
as in Example 9 except that VNB-EPT was replaced by ENB-EPT, and
physical properties thereof were evaluated. The results are listed
in Table 5.
Reference Example 2
[0636] A crosslinked rubber sheet was obtained in the same manner
as in Example 9 except that the compositions (parts by mass) of the
compound in the first step and the compound in the second step were
changed to those listed in Table 5, and physical properties thereof
were evaluated. The results are listed in Table 5.
[0637] Note that PHOSPHANOL RL-210 (TOHO CHEMICAL INDUSTRY Co.,
Ltd.) used in the Examples and Reference Examples is an ester-based
wax, Diak No. 1 (DuPont) is hexamethylene diamine carbamate, and
NOCCELER-DT (Ouchi Shinko Chemical Industrial Co., Ltd.) is
1,3-di-o-tolylguanidine.
[0638] Although this invention relates to a layered product, in
order to evaluate physical properties of each layer constituting a
layered product, a monolayer crosslinked rubber sheet was obtained
and evaluated in Examples 9 and 10 and Reference Example 2.
TABLE-US-00005 TABLE 5 Reference Example Example Example 9 10 2
Composition Formulation First Polymer step VNB-EPT 100 (polymerized
product) Mitsui EPT 2060M 100 (Mitsui Chemicals, Inc.) Vamac G 100
(AEM, DuPont) Compounded agent HAF carbon black 60 60 60 Zinc
flower 5 5 Stearic acid 1 1 1 NOCRAC CD 4.0 4.0 (Ouchi Shinko
Chemical Industrial Co., Ltd.) Second DCP40C 3.4 3.4 step
PHOSPHANOL 1.0 RL-210 (TOHO Chemical Industry Co., Ltd.) Diak No.1
0.5 (DuPont) NOCCELER DT 2.0 (Ouchi Shinko Chemical Industrial Co.,
Ltd.) Test results <Ordinary physical properties> 180.degree.
C. .times. 10-minute vulcanization Hardness (shoreA) 70 71 74
M100[MPa] 1.7 1.5 2.6 M200[MPa] 3.4 2.0 5.3 M300[MPa] 6.2 3.0 7.7
TB[MPa] 15.6 6.3 11.6 EB[%] 619 643 646 <Heat aging
resistance> 180.degree. C. .times. 168 h later Hardness (shoreA)
73 76 85 TB [MPa] 7.8 3.2 7.0 EB [%] 297 129 317 <Demacha
bending fatigue > Ordinary temperature, no >500,000 Cut off
at >500,000 scratch times 300,000 times times Remarks:
Conditions of test No Recess piece recess formed after 100,000
times
Example 11
[0639] (Preparation of Composition Containing VNB-EPT)
[0640] As a first step, 100 parts by mass of VNB-EPT was roughly
kneaded for 1 seconds by a Banbury mixer, Model BB-2 (manufactured
by KOBE STEEL, LTD.), to which copolymer were added 30 parts by
mass of FEF carbon black (Asahi #60G, manufactured by Asahi Carbon
Co., Ltd.), 45 parts by mass of SRF carbon black (Asahi #50G,
manufactured by Asahi Carbon Co., Ltd.), 40 parts by mass of FT
carbon black (Asahi #15HS, manufactured by Asahi Carbon Co., Ltd.),
5 parts by mass of Kyowamag 150 (manufactured by Kyowa Chemical
Industry Co., Ltd., magnesium oxide), 1 part by mass of stearic
acid, and 4 parts by mass of
4,4'-bis(.alpha.,.alpha.-dimethylbenzyl)diphenylamine (NOCRAC CD
manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.), 3
parts by mass of LIPOQUAD 2HT Flake (manufactured by Lion Specialty
Chemicals Co., Ltd.), and 47 parts by mass of Diana Process Oil
PS-430 (manufactured by Idemitsu Kosan Co., Ltd.), and they were
kneaded at 140.degree. C. for 2 minutes. Then, the ram of the mixer
was raised to be cleaned, and they were kneaded for one more
minute, and discharged at about 150.degree. C. to yield a compound
of the first step.
[0641] Next, as a second step, the compound obtained in the first
step was banded on a roll of an 8-inch roll mill (manufactured by
Nippon Roll MFG. Co., Ltd., operating with a front roll at a
surface temperature of 50.degree. C. and a rotational rate of 18
rpm and aback roll at a surface temperature of 50.degree. C. and a
rotational rate of 15 rpm), and 3 parts by mass of master batch
(perhexa 25B-40, Manufactured by NOF Corporation) (1.2 parts by
mass in terms of organic peroxide) containing 40% by mass of
2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane as 3 parts by mass of
the organic peroxide component, and 3 parts by mass of Hi-Cross M
(Seiko Chemical Co., Ltd., a crosslinking aid) were added to the
compound, which was then kneaded for 10 minutes to yield an
uncrosslinked resin composition (rubber compound) (composition
containing VNB-EPT).
[0642] (Composition Containing Fluorine Rubber)
[0643] As a composition containing fluorine rubber, DAI-EL DC-2270F
(manufactured by Daikin Industries, Ltd.: polyol crosslinked-type
fluorine rubber compound) was used. DAI-EL DC-2270F is a
composition containing a polyol-based crosslinking agent (bisphenol
AF), a crosslinking enhancer (quaternary onium salt), a filler, and
an acid acceptor, in addition to fluorine rubber.
[0644] (Preparation and Evaluation of Layered Product)
[0645] (Preparation of Layered Product for T-Peel Test)
[0646] The composition containing VNB-EPT and the composition
containing fluorine rubber were each sheeted into a sheet-like
shape. Next, 100 g of each of the unvulcanized rubber sheets (the
sheets of the composition containing VNB-EPT and the composition
containing fluorine rubber) was sandwiched between LUMIRRORs
(stretched polyester (polyethylene terephthalate) film). Each
unvulcanized rubber sheet sandwiched between LUMIRRORs was pressed
at 120.degree. C. for 2 minutes using a 50-ton press-shaping
machine to prepare a unvulcanized rubber sheet in 20 cm in square
(t (thickness)=1 mm).
[0647] Next, the unvulcanized rubber sheet obtained from the
composition containing VNB-EPT (layer A) and the pressed
unvulcanized rubber sheet obtained from the composition containing
fluorine rubber (layer B) after the press were each cut into the
press size described below (15 cm.times.15 cm x t=1 mm). After
cutting, the upper-side and lower-side LUMIRRORs were removed, and
then the respective unvulcanized rubber sheets were stacked on each
other. The unvulcanized rubber sheets were stacked on each other in
a manner such that a Teflon (registered trademark) resin sheet
(t=0.2 mm) is sandwiched between the unvulcanized rubber sheets at
a certain part (width of 3 cm, length of 15 cm: margin for peel
test).
[0648] The stacked unvulcanized rubber sheets sandwiching the
Teflon (registered trademark) resin sheet at the certain part was
pressed (main press) at 180.degree. C. for 10 minutes using a
100-ton press-shaping machine to prepare a primarily vulcanized
crosslinked rubber sheet (layered product) of 2 mm in
thickness.
[0649] The Teflon (registered trademark) resin sheet was removed
from the resulting crosslinked rubber sheet (layered product), and
the crosslinked rubber sheet (layered product) was placed in an
oven at 180.degree. C. for 4 hours for carrying out secondary
vulcanization to yield a crosslinked rubber sheet (layered
product).
[0650] T-peel test of the secondarily vulcanized crosslinked rubber
sheet (layered product) was conducted.
Example 12
[0651] This Example was conducted in the same manner as in Example
11 except that the compound in the first step was obtained using 20
parts by mass of DHT-4A (manufactured by Kyowa Chemical Industry
Co., Ltd., hydrotalcite compound: Mg.sub.4.3A.sub.12
(OH).sub.12.6CO.sub.3/mH.sub.2O).
Example 13
[0652] This Example was conducted in the same manner as in Example
11 except that the amount of Kyowamag 150 used was changed from 5
parts by mass to 25 parts by mass to obtain the compound in the
first step.
[0653] The formulations of the compositions containing VNB-EPT in
Examples 11 to 13, the composition of containing fluorine rubber,
and the results of T-peel test are listed in Table 6.
TABLE-US-00006 TABLE 6 Example 11 Example 12 Example 13
[Composition formulation containing VNB-EPT] VNB-EPT Parts by 100
100 100 mass LIPOQUAD Parts by 3 3 3 2HT FLAKE mass DHT-4A Parts by
20 mass Kyowamag 150 Parts by 5 5 25 mass Stearic acid Parts by 1 1
1 mass Asahi #60 Parts by 30 30 30 mass Asahi #50 Parts by 45 45 45
mass Asahi #15HS Parts by 40 40 40 mass PS-430 Parts by 47 47 47
mass PERHEXA 25B-40 Parts by 3 3 3 mass Hi-Cross M Parts by 3 3 3
mass NOCRAC CD Parts by 4 4 4 mass Total 281 301 301 Composition
DC-2270F DC-2270F DC-2270F containing fluorine rubber T-peel test
N/cm 12.0 22.2 19.8
* * * * *